Dual metallocene catalysts for polymerization of bimodal polymers

ABSTRACT

This invention relates to catalyst compositions, methods, and polymers encompassing at least one first Group 4 metallocene compound comprising bridging η 5 -cyclopentadienyl-type ligands, in combination with at least one second Group 4 metallocene with non-bridging η 5 -cyclopentadienyl-type ligands, typically in combination with at least one cocatalyst, and at least one activator. The compositions and methods disclosed herein provide ethylene polymers with a bimodal molecular weight distribution.

TECHNICAL FIELD OF THE INVENTION

This invention relates to the field of organometal compositions, olefinpolymerization catalyst compositions, methods for the polymerization andcopolymerization of olefins using a catalyst composition, andpolyolefins.

BACKGROUND OF THE INVENTION

It is known that mono-1-olefins (α-olefins), including ethylene, can bepolymerized with catalyst compositions employing titanium, zirconium,vanadium, chromium, or other metals, often combined with a solid oxideand in the presence of cocatalysts. These catalyst compositions can beuseful for both homopolymerization of ethylene, as well ascopolymerization of ethylene with comonomers such as propylene,1-butene, 1-hexene, or other higher α-olefins. Therefore, there exists aconstant search to develop new olefin polymerization catalysts, catalystactivation processes, and methods of making and using catalysts thatwill provide enhanced catalytic activities and polymeric materialstailored to specific end uses.

A variety of polyethylene (PE) resins can be used to produce highstiffness pipe used in water, gas, and other fluid transportapplications. Polyethylene pipe classified as PE-100, MRS 10, or ASTMD3350 typical cell classification 345566C is desirable for use underconditions requiring higher pressure ratings. To obtain a PE-100classification, PE-100 pipe is required to meet certain standardsspecifying stiffness, resistance to slow crack growth, resistance tochemical attack, and low-temperature toughness (expressed as rapid crackpropagation). Further, such pipe must meet a deformation standard thatis determined under pressure at elevated temperatures, and exhibittoughness for applications in which the pipe is buried underground orused to transport coarse or abrasive slurries.

Accordingly, there is also a need for a resin and a PE-100 pipe madethere from that has improved physical properties and impact resistanceproperties. With conventional processes and resins formed usingmetallocene catalyst systems, there is a trade off between highstiffness and high environmental stress cracking resistance (ESCR).While either high stiffness or high ESCR items can be manufactured,conventional processes do not produce items having both relatively highstiffness and relatively high ESCR.

SUMMARY OF THE INVENTION

This invention encompasses catalyst compositions, methods for preparingcatalyst compositions, methods for polymerizing olefins, and ethylenepolymers and copolymers. In one aspect, the present invention generallyrelates to a catalyst composition including at least two differentmetallocene compounds, optionally at least one organoaluminum compound;and at least one activator. In one aspect, the activator can be an“activator-support”, which is typically used in combination with atleast one organoaluminum co-catalyst. The dual metallocene catalystsystem according to this disclosure can produce a polyolefin having abimodal or multimodal molecular weight distribution. The resultingpolymers feature a good balance of stiffness and slow crack growthresistance. Additionally, the polymers produced according to the presentinvention have good impact strength. Thus, in accordance with thepresent invention, the two metallocene compounds can be selected suchthat the polymers produced therefrom have two distinctly differentmolecular weights.

In one aspect of the present invention, for example, it was found thatcertain metallocene-based catalyst systems could produce high molecularweight polyethylene with low levels of LCB, even under relatively hightemperature conditions. Useful metallocenes in this aspect of theinvention include, but are not limited to, tightly-bridged,ansa-metallocenes that comprise a pendant alkenyl (olefin-containing)group attached to at least one of the cyclopentadienyl-type moieties ofthe tightly-bridged ligand, and also comprises one or two aryl groups,particularly one or two phenyl groups, bonded to the bridging atom ofthe tightly-bridged ligand. These metallocene compounds generally arereferred to herein as the “first” metallocenes.

In another aspect of this invention, for example, it was found thatcertain other metallocene-based catalyst systems were more responsive tohydrogen than the first metallocene, and generally produced a lowmolecular weight polyethylene resin. Useful metallocenes in this aspectof the invention include, but are not limited to, those metallocenescomprising unbridged η⁵-cyclopentadienyl-type ligands selected from: 1)two optionally substituted cyclopentadienyl ligands; 2) two optionallysubstituted indenyl ligands; or 3) one substituted cyclopentadienyl andone optionally substituted indenyl ligand. These metallocene compoundsgenerally are referred to herein as the “second” metallocenes. In afurther aspect, tailoring of resin properties can be achieved using acatalyst composition that includes more than one first metallocene, morethan one second metallocene, or both more than one first and more thanone second metallocene.

Thus, in one aspect, the present invention encompasses a catalystcomposition comprising the contact product of: at least one firstmetallocene, for example, tightly-bridged ansa-metallocene compoundscontaining a pendant olefin-containing moiety attached to at least oneof the cyclopentadienyl-type ligands and one or two aryl groups bondedto the bridging atom of the bridging ligand; at least one secondmetallocene, for example, unbridged metallocenes comprising twooptionally substituted cyclopentadienyl ligands, two optionallysubstituted indenyl ligands, or one substituted cyclopentadienyl and oneoptionally substituted indenyl ligand; optionally, at least oneorganoaluminum compound; and at least one activator. In one aspect, theat least one activator can be an activator-support, which can beselected from, or which can comprise, a solid oxide treated with anelectron-withdrawing anion, a layered mineral, an ion-exchangeableactivator-support, or any combination thereof. In another aspect, the atleast one activator can be be selected from, or can comprise, anorganoaluminoxane compound, an organoboron compound, an organoboratecompound, or any combination of any of these activators. Thus, in thisaspect, this invention encompasses a composition of matter, a catalystcomposition for polymerizing olefins, a method of preparing a catalystcomposition, a method of polymerizing olefins, new polymers andcopolymers of ethylene, and the like, in each case encompassing at leastone first metallocene, at least one second metallocene, optionally atleast one organoaluminum compound, and at least one activator, whereineach of these components is defined as herein.

In another aspect, this invention comprises the contact product of atleast one first metallocene, for example, tightly-bridgedansa-metallocene compounds containing a pendant olefin-containing moietyattached to at least one of the cyclopentadienyl-type ligands and one ortwo aryl groups bonded to the bridging atom of the bridging ligand; atleast one second metallocene, for example, an unbridged metallocenecomprising two optionally substituted cyclopentadienyl ligands, twooptionally substituted indenyl ligands, or one substitutedcyclopentadienyl and one optionally substituted indenyl ligand; at leastone activator-support; and at least one co-catalyst, for example, atleast one organoaluminum compound.

Still another aspect of this invention provides a catalyst compositionof this invention that can comprise the contact product of: 1) at leastone first metallocene; 2) at least one second metallocene; 3)optionally, at least one organoaluminum compound; and 4) at least oneactivator, wherein:

a) the at least one first metallocene comprises an ansa-metallocenehaving the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-A),wherein

-   -   M¹ is titanium, zirconium, or hafnium;    -   (X¹) and (X²) are independently a substituted cyclopentadienyl,        a substituted indenyl, or a substituted fluorenyl;    -   one substituent on (X¹) and (X²) is a bridging group having the        formula ER¹R², wherein E is a carbon atom, a silicon atom, a        germanium atom, or a tin atom, and E is bonded to both (X¹) and        (X²), and wherein R¹ and R² are independently an alkyl group or        an aryl group, either of which having up to 12 carbon atoms, or        hydrogen, wherein at least one of R¹ and R² is an aryl group;    -   at least one substituent on (X¹) or (X²) is a substituted or an        unsubstituted alkenyl group having up to 12 carbon atoms;    -   (X³) and (X⁴) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; and    -   any additional substituent on the substituted cyclopentadienyl,        substituted indenyl, substituted fluorenyl, or substituted        alkenyl group is independently an aliphatic group, an aromatic        group, a cyclic group, a combination of aliphatic and cyclic        groups, an oxygen group, a sulfur group, a nitrogen group, a        phosphorus group, an arsenic group, a carbon group, a silicon        group, or a boron group, any of which having from 1 to 20 carbon        atoms; a halide; or hydrogen;

b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-A),wherein

-   -   M² is titanium, zirconium, or hafnium;    -   (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,        a substituted cyclopentadienyl, or a substituted indenyl;    -   (X⁷) and (X⁸) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(B) ₂ or SO₃R^(B), wherein R^(B) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; and    -   any substituent on the substituted cyclopentadienyl or        substituted indenyl is independently an aliphatic group, an        aromatic group, a cyclic group, a combination of aliphatic and        cyclic groups, an oxygen group, a sulfur group, a nitrogen        group, a phosphorus group, an arsenic group, a carbon group, a        silicon group, or a boron group, any of which having from 1 to        20 carbon atoms; a halide; or hydrogen;        ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-A),        wherein    -   M³ is titanium, zirconium, or hafnium;    -   (X⁹) is a substituted cyclopentadienyl group, wherein one        substituent is an aliphatic group, an aromatic group, or a        combination of aliphatic and cyclic groups, any of which having        up to 20 carbon atoms;    -   (X¹⁰) is a substituted indenyl group, wherein one substituent is        an aliphatic group, an aromatic group, or a combination of        aliphatic and cyclic groups, any of which having up to 20 carbon        atoms;    -   (X¹¹) and (X¹²) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(C) ₂ or SO₃R^(C), wherein R^(C) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; and    -   any additional substituent on the substituted cyclopentadienyl        or substituted indenyl is independently an aliphatic group, an        aromatic group, a cyclic group, a combination of aliphatic and        cyclic groups, an oxygen group, a sulfur group, a nitrogen        group, a phosphorus group, an arsenic group, a carbon group, a        silicon group, or a boron group, any of which having from 1 to        20 carbon atoms; a halide; or hydrogen;

or

-   -   iii) any combination thereof;

c) the at least one organoaluminum compound comprises a compound havingthe formula:Al(X¹³)_(n)(X¹⁴)_(3-n),

-   -   wherein (X¹³) is a hydrocarbyl having from 1 to 20 carbon atoms;        (X¹⁴) is an alkoxide or an aryloxide, any of which having from 1        to 20 carbon atoms, halide, or hydride; and n is a number from 1        to 3, inclusive; and

d) the at least one activator is selected independently from:

-   -   i) an activator-support selected from a solid oxide treated with        an electron-withdrawing anion, a layered mineral, an        ion-exchangeable activator-support, or any combination thereof;    -   ii) an organoaluminoxane compound;    -   iii) an organoboron compound or an organoborate compound; or    -   iv) any combination thereof.

In one aspect of this invention, the at least one organoaluminumcompound can be optional when at least one of the following conditionsis met:

1) when: a) at least one of (X³) and (X⁴) is a hydrocarbyl group havingup to 20 carbon atoms, H, or BH₄; b) at least one of (X⁷) and (X⁸) is ahydrocarbyl group having up to 20 carbon atoms, H, or BH₄; and c) atleast one of (X¹¹) and (X¹²) is a hydrocarbyl group having up to 20carbon atoms, H, or BH₄;

2) when the at least one activator comprises at least oneorganoaluminoxane compound; or

3) when both conditions 1 and 2 are met.

Another aspect of this invention provides a composition that comprisesthe contact product of: 1) at least one first metallocene; 2) at leastone second metallocene; and 3) at least one activator, wherein each ofthese components is as disclosed immediately above. In still anotheraspect of this composition, the contact product can further comprise: 4)at least one organoaluminum compound having the formulaAl(X¹³)_(n)(X¹⁴)_(3-n), as provide above. In another aspect of thiscomposition, the contact product can further comprise: 5) an ionizingionic compound, as disclosed herein.

Yet another aspect of this invention provides a catalyst compositionthat can comprise the contact product of: 1) at least one firstmetallocene; 2) at least one second metallocene; 3) optionally, at leastone organoaluminum compound; and 4) at least one activator, wherein:

a) the at least one first metallocene comprises an ansa-metallocenehaving the formula (M1-A) provided herein;

b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-B),wherein

-   -   M² is zirconium or hafnium;    -   (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,        a substituted cyclopentadienyl, or a substituted indenyl;    -   (X⁷) and (X⁸) are independently a hydrocarbyl group having up to        12 carbon atoms, H, BH₄, or a halide; and    -   any substituent on the substituted cyclopentadienyl or        substituted indenyl is independently an aliphatic group, an        aromatic group, a cyclic group, a combination of aliphatic and        cyclic groups, any of which having up to 20 carbon atoms;        ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-B),        wherein    -   M³ is zirconium or hafnium;    -   (X⁹) is a substituted cyclopentadienyl group, wherein any        substituent is independently a linear or branched alkyl group        having up to 12 carbon atoms;    -   (X¹⁰) is a substituted indenyl group, wherein any substituent is        independently an aliphatic group, an aromatic group, or a        combination of aliphatic and cyclic groups, any of which having        up to 20 carbon atoms; and    -   (X¹¹) and (X¹²) are independently a hydrocarbyl group having up        to 12 carbon atoms, H, BH₄, or a halide;

or

-   -   iii) any combination thereof;

c) the at least one organoaluminum compound comprises a compound havingthe formula:Al(X¹³)_(n)(X¹⁴)_(3-n),

-   -   wherein (X¹³) is a hydrocarbyl having from 1 to 20 carbon atoms;        (X¹⁴) is an alkoxide or an aryloxide, any of which having from 1        to 20 carbon atoms, halide, or hydride; and n is a number from 1        to 3, inclusive; and

d) the at least one activator is selected independently from:

-   -   i) an activator-support selected from a solid oxide treated with        an electron-withdrawing anion, a layered mineral, an        ion-exchangeable activator-support, or any combination thereof;    -   ii) an organoaluminoxane compound;    -   iii) an organoboron compound or an organoborate compound; or    -   iv) any combination thereof.

Also in this aspect of the invention, the at least one organoaluminumcompound can be optional when at least one of the following conditionsis met:

1) when: a) at least one of (X³) and (X⁴) is a hydrocarbyl group havingup to 20 carbon atoms, H, or BH₄; b) at least one of (X⁷) and (X⁸) is ahydrocarbyl group having up to 20 carbon atoms, H, or BH₄; and c) atleast one of (X¹¹) and (X¹²) is a hydrocarbyl group having up to 20carbon atoms, H, or BH₄;

2) when the at least one activator comprises at least oneorganoaluminoxane compound; or

3) when both conditions 1 and 2 are met.

While not intending to be bound by theory, it will be recognized by oneof ordinary skill that a metallocene-based composition that exhibitscatalytic polymerization activity typically comprises the contactproduct of: 1) at least one metallocene component; 2) a co-catalystcomponent that provides an activatable ligand such as an alkyl orhydride ligand to the metallocene, when the metallocene compound orcompounds do not already comprise such a ligand; and 3) an activatorcomponent. In some instances, one component can function as both thecomponent that provides an activatable ligand and the activatorcomponent, for example, an organoaluminoxane can function in both ways.In other cases, these two functions can be provided by two separatecomponents, such as an organoaluminum compound that can provide anactivatable alkyl ligand to the metallocene, and a solid oxide treatedwith an electron-withdrawing anion that can provide the activatorfunction. Further, in some instances, the metallocene compound canalready comprise an activatable ligand such as an alkyl ligand,therefore, a component that provides an activatable ligand is notrequired, but can be an optional component of the contact product.Therefore, by designating the at least one organoaluminum compound as“optional” in the contact product, it is intended to reflect that theorganoaluminum compound can be optional when it is not necessary toimpart catalytic activity to the composition comprising the contactproduct, as understood by one of ordinary skill.

Thus, a further aspect of this invention provides a catalyst compositioncomprising the contact product of: 1) at least one first metallocene; 2)at least one second metallocene; and 3) at least one activator, wherein:

a) the at least one first metallocene comprises an ansa-metallocenehaving the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-B),wherein

-   -   M¹ is titanium, zirconium, or hafnium;    -   (X¹) and (X²) are independently a substituted cyclopentadienyl,        a substituted indenyl, or a substituted fluorenyl;    -   one substituent on (X¹) and (X²) is a bridging group having the        formula ER¹R², wherein E is a carbon atom, a silicon atom, a        germanium atom, or a tin atom, and E is bonded to both (X¹) and        (X²), and wherein R¹ and R² are independently an alkyl group or        an aryl group, either of which having up to 12 carbon atoms, or        hydrogen, wherein at least one of R¹ and R² is an aryl group;    -   at least one substituent on (X¹) or (X²) is a substituted or an        unsubstituted alkenyl group having up to 12 carbon atoms;    -   (X³) and (X⁴) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; wherein at least one (X³) and (X⁴) is a hydrocarbyl group        having up to 20 carbon atoms, H, or BH₄; and    -   any additional substituent on the substituted cyclopentadienyl,        substituted indenyl, substituted fluorenyl, or substituted        alkenyl group is independently an aliphatic group, an aromatic        group, a cyclic group, a combination of aliphatic and cyclic        groups, an oxygen group, a sulfur group, a nitrogen group, a        phosphorus group, an arsenic group, a carbon group, a silicon        group, or a boron group, any of which having from 1 to 20 carbon        atoms; a halide; or hydrogen;

b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-C),wherein

-   -   M² is titanium, zirconium, or hafnium;    -   (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,        a substituted cyclopentadienyl, or a substituted indenyl;    -   (X⁷) and (X⁸) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; wherein at least one (X⁷) and (X⁷) is a hydrocarbyl group        having up to 20 carbon atoms, H, or BH₄; and    -   any substituent on the substituted cyclopentadienyl or        substituted indenyl is independently an aliphatic group, an        aromatic group, a cyclic group, a combination of aliphatic and        cyclic groups, an oxygen group, a sulfur group, a nitrogen        group, a phosphorus group, an arsenic group, a carbon group, a        silicon group, or a boron group, any of which having from 1 to        20 carbon atoms; a halide; or hydrogen;        ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-C),        wherein    -   M³ is titanium, zirconium, or hafnium;    -   (X⁹) is a substituted cyclopentadienyl group, wherein one        substituent is an aliphatic group, an aromatic group, or a        combination of aliphatic and cyclic groups, any of which having        up to 20 carbon atoms;    -   (X¹⁰) is a substituted indenyl group, wherein one substituent is        an aliphatic group, an aromatic group, or a combination of        aliphatic and cyclic groups, any of which having up to 20 carbon        atoms;    -   (X¹¹) and (X¹²) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; wherein at least one (X¹¹) and (X¹²) is a hydrocarbyl        group having up to 20 carbon atoms, H, or BH₄; and    -   any additional substituent on the substituted cyclopentadienyl        or substituted indenyl is independently an aliphatic group, an        aromatic group, a cyclic group, a combination of aliphatic and        cyclic groups, an oxygen group, a sulfur group, a nitrogen        group, a phosphorus group, an arsenic group, a carbon group, a        silicon group, or a boron group, any of which having from 1 to        20 carbon atoms; a halide; or hydrogen;

or

-   -   iii) any combination thereof; and

c) the at least one activator is selected independently from:

-   -   i) an activator-support selected from a solid oxide treated with        an electron-withdrawing anion, a layered mineral, an        ion-exchangeable activator-support, or any combination thereof;    -   ii) an organoaluminoxane compound;    -   iii) an organoboron compound or an organoborate compound; or    -   iv) any combination thereof.

Still a further aspect of this invention provides a catalyst compositioncomprising the contact product of: 1) at least one first metallocene; 2)at least one second metallocene; and 3) at least one activator, wherein:

a) the at least one first metallocene comprises an ansa-metallocenehaving the formula (M1-B) as provided herein;

b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-D),wherein

-   -   M² is zirconium or hafnium;    -   (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,        a substituted cyclopentadienyl, or a substituted indenyl;    -   (X⁷) and (X⁸) are independently a hydrocarbyl group having up to        12 carbon atoms, H, BH₄, or a halide, wherein at least one of        (X⁷) and (X⁸) is a hydrocarbyl group, H, or BH₄; and    -   any substituent on the substituted cyclopentadienyl or        substituted indenyl is independently an aliphatic group, an        aromatic group, a cyclic group, a combination of aliphatic and        cyclic groups, any of which having up to 20 carbon atoms;        ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-D),        wherein    -   M³ is zirconium or hafnium;    -   (X⁹) is a substituted cyclopentadienyl group, wherein any        substituent is independently a linear or branched alkyl group        having up to 12 carbon atoms;    -   (X¹⁰) is a substituted indenyl group, wherein any substituent is        independently an aliphatic group, an aromatic group, or a        combination of aliphatic and cyclic groups, any of which having        up to 20 carbon atoms; and    -   (X¹¹) and (X¹²) are independently a hydrocarbyl group having up        to 12 carbon atoms, H, BH₄, or a halide, wherein at least one of        (X⁷) and (X⁸) is a hydrocarbyl group, H, or BH₄; or    -   iii) any combination thereof;        and

c) the at least one activator is selected independently from:

-   -   i) an activator-support selected from a solid oxide treated with        an electron-withdrawing anion, a layered mineral, an        ion-exchangeable activator-support, or any combination thereof;    -   ii) an organoaluminoxane compound;    -   iii) an organoboron compound or an organoborate compound; or    -   iv) any combination thereof.

In a further aspect of this invention, the activator-support can be, orcan comprise, a solid oxide treated with an electron-withdrawing anion,wherein the solid oxide comprises silica, alumina, silica-alumina,aluminophosphate, aluminum phosphate, zinc aluminate,heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or mixtures thereof. In this aspect, theelectron-withdrawing anion can comprise fluoride, chloride, bromide,iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate,fluorosulfate, trifluoroacetate, phosphate, fluorophosphate,fluorozirconate, fluorosilicate, fluorotitanate, permanganate,substituted or unsubstituted alkanesulfonate, substituted orunsubstituted arenesulfonate, or any combination thereof. In addition,the activator-support can further comprise a metal or metal ion such aszinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or anycombination thereof. Also in this aspect, the electron-withdrawing anioncan be fluoride, chloride, bromide, iodide, phosphate, triflate,bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate,phosphate, fluorophosphate, fluorozirconate, fluorosilicate,fluorotitanate, permanganate, substituted or unsubstitutedalkanesulfonate, substituted or unsubstituted arenesulfonate, and thelike, including any combination thereof.

In yet another aspect of this invention, the activator-support can be,or can comprise, a layered mineral, an ion-exchangeableactivator-support, or any combination of these activator-supports,including any combination of these activator-supports with a solid oxidetreated with an electron-withdrawing anion. In this aspect, theactivator-support can comprise a clay mineral, a pillared clay, anexfoliated clay, an exfoliated clay gelled into another oxide matrix, alayered silicate mineral, a non-layered silicate mineral, a layeredaluminosilicate mineral, a non-layered aluminosilicate mineral, or anycombination thereof.

In another aspect, this invention further provides a process forproducing a polymerization catalyst composition comprising contacting atleast one first metallocene, at least one second metallocene, optionallyat least one organoaluminum compound, and at least one activator, toproduce the catalyst composition, wherein the at least one firstmetallocene, the at least one second metallocene, the at least oneorganoaluminum compound, and the at least one activator are defined asherein. In still another aspect, this invention affords a method ofpolymerizing olefins, comprising contacting ethylene and an optionalα-olefin comonomer with a catalyst composition as provided herein underpolymerization conditions to form a polymer or copolymer. In yet furtheraspect, the present invention provides ethylene polymers and copolymers,and articles made therefrom, produced by contacting ethylene and anoptional α-olefin comonomer with a catalyst composition underpolymerization conditions to form a polymer or copolymer; wherein thecatalyst composition is provided as disclosed herein.

In still another aspect of this disclosure, the activity of the catalystcompositions of this invention can be enhanced by precontacting some ofthe polymerization reaction components to form a first mixture, for afirst period of time, before this mixture is then contacted with theremaining polymerization reaction components, forming a second mixture,for a second period of time. For example, the first metallocenecompound, the second metallocene compound, or both the first and secondmetallocene compounds can be precontacted with various otherpolymerization reaction components, including but not limited to, forexample, an α-olefin monomer and optionally an organoaluminumcocatalyst, for some period of time before this mixture is contactedwith the remaining polymerization reaction components, including, butnot limited to, an activator-support. In this aspect, the first mixtureis typically termed the “precontacted” mixture and comprisesprecontacted components, and the second mixture is typically termed the“postcontacted” mixture and comprises postcontacted components.

For example, the mixture of at least one first metallocene, at least onesecond metallocene, olefin monomer, and organoaluminum cocatalystcompound, before it is contacted with the activator-support, is one typeof “precontacted” mixture. Precontacting catalyst composition componentscan also occur in more than one step, giving rise to a firstprecontacted mixture, a second precontacted mixture, and the like. Onceall catalyst composition components are in contact, this mixture istermed the “postcontacted” mixture. For example, once a mixture of firstmetallocene, second metallocene, monomer, organoaluminum cocatalyst, andactivator-support has been formed from contacting any remaining catalystcomponents with the final precontacted mixture, this mixture is termedthe “postcontacted” mixture. This terminology is used regardless of whattype of reaction, if any, occurs between components of the mixtures. Forexample, according to this description, it is possible for theprecontacted organoaluminum compound, once it is admixed with themetallocene or metallocenes and the olefin monomer, to have a differentchemical formulation and structure from the distinct organoaluminumcompound used to prepare the precontacted mixture.

This invention also comprises methods of making catalyst compositionsthat utilize at least one first metallocene, at least one secondmetallocene, at least one optional cocatalyst, such as an aluminoxane,and at least one activator, wherein each of these components isdisclosed herein. The methods of this invention include precontactingany selected catalyst components, for example, the first or secondmetallocene or both the first and second metallocene, optionally with anorganoaluminum cocatalyst and optionally with an olefin, typically butnot necessarily, a monomer to be polymerized or copolymerized, prior tocontacting this precontacted mixture with any remaining catalystcomponents, in this example, the activator, such as anactivator-support.

The present invention further comprises new catalyst compositions,methods for preparing catalyst compositions, and methods forpolymerizing olefins that result in improved productivity. In oneaspect, these methods can be carried out without the need for usinglarge excess concentrations of the expensive cocatalyst methylaluminoxane (MAO), or the catalyst composition can be substantially freeof MAO. That is, the catalyst compositions of this invention havepolymerization activity in the substantial absence of aluminoxanes.However, this invention also provides a catalyst composition comprisingthe contact product of a first metallocene, a second metallocene, and analuminoxane. In this aspect, the catalyst composition is not required tocomprise an activator-support, wherein the activator-support comprises achemically-treated solid oxide, and the catalyst composition is also notrequired to comprise an organoaluminum compound.

Additionally, this invention encompasses a process comprising contactingat least one monomer and the catalyst composition under polymerizationconditions to produce the polymer. Thus, in one aspect, this inventionprovides methods for polymerizing olefins using the catalystcompositions prepared as described herein.

The present invention also encompasses new polyolefins.

This invention also provides an article that comprises the polymerproduced with the catalyst composition of this invention.

These and other features, aspects, embodiments, and advantages of thepresent invention will become apparent after a review of the followingdetailed description of the disclosed features.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates the formulas of some specific metallocenes that canbe used in this invention, as provided in the Examples.

FIG. 2 provides comparison gel permeation chromatograms (GPCs) forethylene homopolymers and copolymers of Examples 1-6 (E1-E6), preparedas provided in Table 1.

FIG. 3 provides comparison gel permeation chromatograms (GPCs) forethylene copolymers prepared according to inventive Examples 7-13(E7-E13), prepared as provided in Table 2.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new compositions, new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, olefin polymers,and various articles prepared from olefin polymers. In one aspect, thisinvention encompasses a catalyst composition comprising: at least onefirst metallocene, for example, tightly-bridged ansa-metallocenecompounds containing a pendant olefin-containing moiety attached to atleast one of the cyclopentadienyl-type ligands and one or two arylgroups bonded to the bridging atom of the bridging ligand; at least onesecond metallocene, for example, an unbridged metallocene comprising twooptionally substituted cyclopentadienyl ligands, two optionallysubstituted indenyl ligands, or one substituted cyclopentadienyl and oneoptionally substituted indenyl ligand; optionally, at least oneorganoaluminum cocatalyst; and at least one activator. In one aspect,the activator can comprise an activator-support that is used along withan organoaluminum cocatalyst. Also in this aspect, this inventionencompasses a catalyst composition comprising the contact product of thecatalyst components disclosed herein.

In one aspect, the present invention provides a catalyst compositioncomprising the contact product of: 1) at least one first metallocene; 2)at least one second metallocene; 3) optionally, at least oneorganoaluminum compound; and 4) at least one activator, wherein:

a) the at least one first metallocene comprises a compound having theformula:

-   -   M^(1A) is zirconium or hafnium;    -   X^(3A) and X^(4A) are independently F, Cl, Br, I, benzyl,        phenyl, or methyl;    -   E^(A) is C or Si;    -   R^(1A) and R^(2A) are independently an alkyl group or an aryl        group, either of which having up to 12 carbon atoms, or        hydrogen, wherein at least one of R^(1A) or R^(2A) is an aryl        group;    -   R^(3A) and R^(4A) are independently a hydrocarbyl group or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or hydrogen;    -   n is an integer from 0 to 10, inclusive; and    -   R^(5A) and R^(6A) are independently a hydrocarbyl group having        up to 12 carbon atoms, or hydrogen;

b) the at least one second metallocene comprises a compound having theformula:

-   -   i)

-   -    or a combination thereof, wherein        -   M^(2A) is, independently, zirconium or hafnium;        -   X^(7A) and X^(8A), in each occurrence, are independently F,            Cl, Br, I, benzyl, phenyl, or methyl; and        -   R^(7A) and R^(8A), in each occurrence, are independently H,            methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH₂CH₂CH₂Ph,            CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂;    -   ii)

-   -    wherein        -   M^(3A) is zirconium or hafnium;        -   R^(9A) is H or CH₃;        -   R^(10A) is H, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂CH═CH₂,            CH₂CH₂CH₂Ph, or CH₂CH₂CH₂CH₃; and        -   X^(11A) and X^(12A) are independently F, Cl, Br, I, benzyl,            phenyl, or methyl;

or

-   -   iii) any combination thereof;

c) the at least one organoaluminum compound comprises trimethylaluminum,triethylaluminum, tripropylaluminum, tributylaluminum,triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminumethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or anycombination thereof; and

d) the at least one activator is an activator-support comprising a solidoxide treated with an electron-withdrawing anion, wherein:

-   -   the solid oxide is silica, alumina, silica-alumina,        aluminophosphate, aluminum phosphate, zinc aluminate,        heteropolytungstates, titania, zirconia, magnesia, boria, zinc        oxide, mixed oxides thereof, or any combination thereof; and    -   the electron-withdrawing anion is fluoride, chloride, bromide,        iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate,        fluorosulfate, trifluoroacetate, phosphate, fluorophosphate,        fluorozirconate, fluorosilicate, fluorotitanate, permanganate,        substituted or unsubstituted alkanesulfonate, substituted or        unsubstituted arenesulfonate, or any combination thereof.

Yet another aspect of this invention provides a catalyst compositioncomprising the contact product of: 1) at least one first metallocene; 2)at least one second metallocene; and 3) at least one activator, wherein:

a) the at least one first metallocene comprises a compound having theformula:

wherein

-   -   M^(1A) is zirconium or hafnium;    -   X^(3A) and X^(4A) are independently F, Cl, Br, I, benzyl,        phenyl, or methyl, wherein at least one of X^(3A) and X^(4A) is        benzyl, phenyl, or methyl;    -   E^(A) is C or Si;    -   R^(1A) and R^(2A) are independently an alkyl group or an aryl        group, either of which having up to 12 carbon atoms, or        hydrogen, wherein at least one of R^(1A) or R^(2A) is an aryl        group;    -   R^(3A) and R^(4A) are independently a hydrocarbyl group or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or hydrogen;    -   n is an integer from 0 to 10, inclusive; and    -   R^(5A) and R^(6A) are independently a hydrocarbyl group having        up to 12 carbon atoms, or hydrogen;

b) the at least one second metallocene comprises a compound having theformula:

-   -   i)

-   -    or a combination thereof, wherein        -   M^(2A) is, independently, zirconium or hafnium;        -   X^(7A) and X^(8A), in each occurrence, are independently F,            Cl, Br, I, benzyl, phenyl, or methyl, wherein at least one            of X^(7A) and X^(8A) is benzyl, phenyl, or methyl; and        -   R^(7A) and R^(8A), in each occurrence, are independently H,            methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH₂CH₂CH₂Ph,            CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂;    -   ii)

-   -    wherein        -   M^(3A) is zirconium or hafnium;        -   R^(9A) is H or CH₃;        -   R^(10A) is H, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂CH═CH₂,            CH₂CH₂CH₂Ph, or CH₂CH₂CH₂CH₃; and        -   X^(11A) and X^(12A) are independently F, Cl, Br, I, benzyl,            phenyl, or methyl, wherein at least one of X^(11A) and            X^(12A) is benzyl, phenyl, or methyl;

or

-   -   iii) any combination thereof; and

c) the at least one activator is an activator-support comprising a solidoxide treated with an electron-withdrawing anion, wherein:

-   -   the solid oxide is silica, alumina, silica-alumina,        aluminophosphate, aluminum phosphate, zinc aluminate,        heteropolytungstates, titania, zirconia, magnesia, boria, zinc        oxide, mixed oxides thereof, or any combination thereof; and    -   the electron-withdrawing anion is fluoride, chloride, bromide,        iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate,        fluorosulfate, trifluoroacetate, phosphate, fluorophosphate,        fluorozirconate, fluorosilicate, fluorotitanate, permanganate,        substituted or unsubstituted alkanesulfonate, substituted or        unsubstituted arenesulfonate, or any combination thereof.        Catalyst Composition and Components

The present invention provides, in one aspect, a catalyst compositioncomprising the contact product of at least one first metallocene, atleast one second metallocene, at least one activator-support; andoptionally, at least one co-catalyst. Each of these components isfurther described below.

The First Metallocene Compound

In one aspect, the first metallocene of the present invention istypically a tightly-bridged ansa-metallocene compound containing apendant olefin-containing moiety attached to at least one of thecyclopentadienyl-type ligands, and also containing one or two arylgroups bonded to the bridging atom of the bridging ligand. As usedherein, the term bridged or ansa-metallocene refers simply to ametallocene compound in which the two η⁵-cycloalkadienyl-type ligands inthe molecule are linked by a bridging moiety, and these term may be usedinterchangeably with the term first metallocene throughout. Usefulansa-metallocenes are typically “tightly-bridged”, meaning that the twoη⁵-cycloalkadienyl-type ligands are connected by a bridging groupwherein the shortest link of the bridging moiety between theη⁵-cycloalkadienyl-type ligands is a single atom. Thus, the length ofthe bridge or the chain between the two η⁵-cycloalkadienyl-type ligandsis one atom, although this bridging atom is substituted. Therefore, thefirst metallocene of this invention typically comprises bridgedbis(η⁵-cycloalkadienyl)-type compounds, wherein the η⁵-cycloalkadienylportions include substituted cyclopentadienyl ligands, substitutedindenyl ligands, substituted fluorenyl ligands, and the like, whereinone substituent on these cyclopentadienyl-type ligands is a bridginggroup having the formula ER¹R², wherein E is a carbon atom, a siliconatom, a germanium atom, or a tin atom, and wherein E is bonded to bothcyclopentadienyl-type ligands. In this aspect, R¹ and R² can be selectedindependently from an alkyl group or an aryl group, either of whichhaving up to 12 carbon atoms, or hydrogen, wherein at least one of R¹and R² is an aryl group.

In this aspect, one substituent on the metallocene'scyclopentadienyl-type ligands can be a bridging group having the formula>CR¹R², >SiR¹R², >GeR¹R², or >SnR¹R², wherein R¹ and R² can beindependently selected from an alkyl group or an aryl group, either ofwhich having up to 12 carbon atoms, or hydrogen, wherein at least one ofR¹ and R² is an aryl group. Examples of bridging ER¹R² groups include,but are not limited to, >CPh₂, >SiPh₂, >GePh₂, >SnPh₂, >C(tolyl)₂,>Si(tolyl)₂, >Ge(tolyl)₂,>Sn(tolyl)₂, >CMePh, >SiMePh, >GeMePh, >SnMePh, >CEtPh, >CPrPh, >CBuPh, >CMe(tolyl), >SiMe(tolyl), >GeMe(tolyl), >SnMe(tolyl), >CHPh, >CH(tolyl),and the like.

Further, at least one substituent on at least one of theη⁵-cycloalkadienyl-type ligands is a substituted or an unsubstitutedolefin-containing hydrocarbyl group, having up to 12 carbon atoms, whichis referred to herein as an “alkenyl group,” regardless of theregiochemistry of the alkene functionality. In this aspect, thisolefin-containing hydrocarbyl group is bonded to one of theη⁵-cycloalkadienyl-type ligands of the bridging ligand, wherein theolefinic bond is distal from the η⁵-cycloalkadienyl-type ligand, andtherefore can be described as a pendant alkenyl group. Thus, onesubstituent on a substituted cyclopentadienyl, a substituted indenyl, ora substituted fluorenyl of the metallocene comprises an alkenyl group,in which case the ansa-metallocenes can be described as containing ahydrocarbyl chain attached to one of the cyclopentadienyl-type ligandswhich comprises an olefinic portion.

Thus, in one aspect, the at least one first metallocene comprises anansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-A),wherein

-   -   M¹ is titanium, zirconium, or hafnium;    -   (X¹) and (X²) are independently a substituted cyclopentadienyl,        a substituted indenyl, or a substituted fluorenyl;    -   one substituent on (X¹) and (X²) is a bridging group having the        formula ER¹R², wherein E is a carbon atom, a silicon atom, a        germanium atom, or a tin atom, and E is bonded to both (X¹) and        (X²), and wherein R¹ and R² are independently an alkyl group or        an aryl group, either of which having up to 12 carbon atoms, or        hydrogen, wherein at least one of R¹ and R² is an aryl group;    -   at least one substituent on (X¹) or (X²) is a substituted or an        unsubstituted alkenyl group having up to 12 carbon atoms;    -   (X³) and (X⁴) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; and    -   any additional substituent on the substituted cyclopentadienyl,        substituted indenyl, substituted fluorenyl, or substituted        alkenyl group is independently an aliphatic group, an aromatic        group, a cyclic group, a combination of aliphatic and cyclic        groups, an oxygen group, a sulfur group, a nitrogen group, a        phosphorus group, an arsenic group, a carbon group, a silicon        group, or a boron group, any of which having from 1 to 20 carbon        atoms; a halide; or hydrogen.

In another aspect, the at least one first metallocene comprises anansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-B),wherein

-   -   M¹ is titanium, zirconium, or hafnium;    -   (X¹) and (X²) are independently a substituted cyclopentadienyl,        a substituted indenyl, or a substituted fluorenyl;    -   one substituent on (X¹) and (X²) is a bridging group having the        formula ER¹R², wherein E is a carbon atom, a silicon atom, a        germanium atom, or a tin atom, and E is bonded to both (X¹) and        (X²), and wherein R¹ and R² are independently an alkyl group or        an aryl group, either of which having up to 12 carbon atoms, or        hydrogen, wherein at least one of R¹ and R² is an aryl group;    -   at least one substituent on (X¹) or (X²) is a substituted or an        unsubstituted alkenyl group having up to 12 carbon atoms;    -   (X³) and (X⁴) are independently: 1) F, Cl, Br, or I; 2) a        hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) a        hydrocarbyloxide group, a hydrocarbylamino group, or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl        group or an aryl group, any of which having up to 12 carbon        atoms; wherein at least one (X³) and (X⁴) is a hydrocarbyl group        having up to 20 carbon atoms, H, or BH₄; and    -   any additional substituent on the substituted cyclopentadienyl,        substituted indenyl, substituted fluorenyl, or substituted        alkenyl group is independently an aliphatic group, an aromatic        group, a cyclic group, a combination of aliphatic and cyclic        groups, an oxygen group, a sulfur group, a nitrogen group, a        phosphorus group, an arsenic group, a carbon group, a silicon        group, or a boron group, any of which having from 1 to 20 carbon        atoms; a halide; or hydrogen.

Further to this aspect, the at least one first metallocene can alsocomprise any combination of metallocenes having the formula(X¹)(X²)(X³)(X⁴)M¹, wherein the substituents and the metals are definedabove. That is, the at least one first metallocene can comprise any ofcombination of (M1-A) and (M2-B).

In another aspect of the present invention, that alkenyl group, that is,the olefin-containing hydrocarbyl group is bonded to one of theη⁵-cycloalkadienyl-type ligands of the first metallocene's bridgingligand, can have up to about 20 carbon atoms. In another aspect, thealkenyl group can have up to about 12 carbon atoms, up to about 8 carbonatoms, or up to about 6 carbon atoms. Examples of alkenyl groupsinclude, but are not limited to, butenyl, pentenyl, hexenyl, heptenyl,or octenyl. In another aspect, the alkenyl group is 3-butenyl or4-pentenyl. Thus, in one aspect, the pendant unsaturated group cancontain the carbon-carbon double bond from about 3 to about 7 carbonatoms removed from the cyclopentadienyl-type ligand itself, and inanother aspect, from 3 to about 4 carbon atoms removed from thecyclopentadienyl-type ligand itself.

In still another aspect, the olefin-containing hydrocarbyl group, thatis the alkenyl group, can be substituted or unsubstituted. For example,any substituent on the alkenyl group, when present, can be selectedindependently from an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, an oxygen group, asulfur group, a nitrogen group, a phosphorus group, an arsenic group, acarbon group, a silicon group, a germanium group, a tin group, a leadgroup, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any of whichhaving from 1 to about 20 carbon atoms; a halide; or hydrogen. Hydrogenis listed as a possible substituent on the alkenyl group in the contextthat hydrogen can add to an unsaturated moiety within the alkenyl group,as long as it does not destroy the alkenyl group. Thus, hydrogen is apossible substituent on any unsaturated moiety within the alkenyl groupso long as it does not add across the very olefin moiety necessary forthis group to be considered an alkenyl group. Further, this descriptionof other substituents on the alkenyl group atom can include substituted,unsubstituted, branched, linear, or heteroatom-substituted analogs ofthese moieties.

Examples of olefinic hydrocarbyl groups, specifically alkenyl groups,that can be bonded to at least one cyclopentadienyl-type moiety include,but are not limited to, 3-butenyl (—CH₂CH₂CH═CH₂), 4-pentenyl(—CH₂CH₂CH₂CH═CH₂), 5-hexenyl (—CH₂CH₂CH₂CH₂CH═CH₂), 6-heptenyl(—CH₂CH₂CH₂CH₂CH₂CH═CH₂), 7-octenyl (—CH₂CH₂CH₂CH₂CH₂CH₂CH═CH₂),3-methyl-3-butenyl [—CH₂CH₂C(CH₃)═CH₂], 4-methyl-3-pentenyl[—CH₂CH₂CH═C(CH₃)₂], 1,1-dimethyl-3-butenyl [—C(CH₃)₂CH₂CH═CH₂],1,1-dimethyl-4-pentenyl [—C(CH₃)₂CH₂CH₂CH═CH₂], and the like, or anysubstituted analog thereof. In one aspect, the unsaturated group bondedto the bridging group can be 3-butenyl (—CH₂CH₂CH═CH₂), 4-pentenyl(—CH₂CH₂CH₂CH═CH₂), or a substituted analog thereof.

In addition to containing a bridging group having the formula ER¹R² andat least one an alkenyl group as disclosed herein, thecyclopentadienyl-type ligands of the first metallocene can also haveother substituents. For example, these substituents can be selected fromthe same chemical groups or moieties that can serve as the (X³) and (X⁴)ligands of the first metallocene. Thus, any additional substituent onthe cyclopentadienyl-type ligands; and any substituent on thesubstituted alkenyl group; and (X³) and (X⁴) can be independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any of which having from 1to about 20 carbon atoms; a halide; or hydrogen; as long as these groupsdo not terminate the activity of the catalyst composition. Further, thislist includes substituents that can be characterized in more than one ofthese categories such as benzyl. This list also includes hydrogen,therefore the notion of a substituted indenyl and substituted fluorenylincludes partially saturated indenyls and fluorenyls including, but notlimited to, tetrahydroindenyl groups, tetrahydrofluorenyl groups, andoctahydrofluorenyl groups.

Examples of each of these substituent groups include, but are notlimited to, the following groups. In each example presented below inwhich R is used in a generic fashion, unless otherwise specified, R isindependently selected from: an aliphatic group; an aromatic group; acyclic group; any combination thereof; any substituted derivativethereof, including but not limited to, a halide-, an alkoxide-, or anamide-substituted analog or derivative thereof; any of which has from 1to about 20 carbon atoms; or hydrogen. Also included in these groups areany unsubstituted, branched, or linear analogs thereof.

Examples of aliphatic groups, in each occurrence, include, but are notlimited to, an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclicgroup, and the like, and includes all substituted, unsubstituted,branched, and linear analogs or derivatives thereof, in each occurrencehaving from one to about 20 carbon atoms. Thus, aliphatic groupsinclude, but are not limited to, hydrocarbyls such as paraffins andalkenyls. For example, aliphatic groups as used herein include methyl,ethyl, propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, amyl, isoamyl,hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl,pentenyl, butenyl, and the like.

Examples of aromatic groups, in each occurrence, include, but are notlimited to, phenyl, naphthyl, anthracenyl, and the like, includingsubstituted derivatives thereof, in each occurrence having from 6 toabout 25 carbons. Substituted derivatives of aromatic compounds include,but are not limited to, tolyl, xylyl, mesityl, and the like, includingany heteroatom substituted derivative thereof.

Examples of cyclic groups, in each occurrence, include, but are notlimited to, cycloparaffins, cycloolefins, cycloacetylenes, arenes suchas phenyl, bicyclic groups and the like, including substitutedderivatives thereof, in each occurrence having from about 3 to about 20carbon atoms. Thus heteroatom-substituted cyclic groups such as furanylare included herein.

In each occurrence, aliphatic and cyclic groups are groups comprising analiphatic portion and a cyclic portion, examples of which include, butare not limited to, groups such as: —(CH₂)_(m)C₆H_(q)R_(5-q) wherein mis an integer from 1 to about 10, and q is an integer from 1 to 5,inclusive; —(CH₂)_(m)C₆H_(q)R_(11-q) wherein m is an integer from 1 toabout 10, and q is an integer from 1 to 11, inclusive; or—(CH₂)_(m)C₅H_(q)R_(9-q) wherein m is an integer from 1 to about 10, andq is an integer from 1 to 9, inclusive. In each occurrence and asdefined above, R is independently selected from: an aliphatic group; anaromatic group; a cyclic group; any combination thereof; any substitutedderivative thereof, including but not limited to, a halide-, analkoxide, or an amide-substituted derivative or analog thereof; any ofwhich has from 1 to about 20 carbon atoms; or hydrogen. In one aspect,aliphatic and cyclic groups include, but are not limited to: —CH₂C₆H₅;—CH₂C₆H₄F; —CH₂C₆H₄Cl; —CH₂C₆H₄Br; —CH₂C₆H₄I; —CH₂C₆H₄OMe; —CH₂C₆H₄OEt;—CH₂C₆H₄NH₂; —CH₂C₆H₄NMe₂; —CH₂C₆H₄NEt₂; —CH₂CH₂C₆H₅; —CH₂CH₂C₆H₄F;—CH₂CH₂C₆H₄Cl; —CH₂CH₂C₆H₄Br; —CH₂CH₂C₆H₄I; —CH₂CH₂C₆H₄OMe;—CH₂CH₂C₆H₄OEt; —CH₂CH₂C₆H₄NH₂; —CH₂CH₂C₆H₄NMe₂; —CH₂CH₂C₆H₄NEt₂; anyregioisomer thereof, and any substituted derivative thereof.

Examples of halides, in each occurrence, include fluoride, chloride,bromide, and iodide.

In each occurrence, oxygen groups are oxygen-containing groups, examplesof which include, but are not limited to, alkoxy or aryloxy groups (—OR)and the like, including substituted derivatives thereof, wherein R isalkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl,or substituted aralkyl having from 1 to about 20 carbon atoms. Examplesof alkoxy or aryloxy groups (—OR) groups include, but are not limitedto, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, andthe like.

In each occurrence, sulfur groups are sulfur-containing groups, examplesof which include, but are not limited to, —SR and the like, includingsubstituted derivatives thereof, wherein R in each occurrence is alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

In each occurrence, nitrogen groups are nitrogen-containing groups,which include, but are not limited to, —NR₂ or pyridyl groups, and thelike, including substituted derivatives thereof, wherein R in eachoccurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl having from 1 to about 20carbon atoms.

In each occurrence, phosphorus groups are phosphorus-containing groups,which include, but are not limited to, —PR₂, and the like, includingsubstituted derivatives thereof, wherein R in each occurrence is alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

In each occurrence, arsenic groups are arsenic-containing groups, whichinclude, but are not limited to, —AsR₂, and the like, includingsubstituted derivatives thereof, wherein R in each occurrence is alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

In each occurrence, carbon groups are carbon-containing groups, whichinclude, but are not limited to, alkyl halide groups that comprisehalide-substituted alkyl groups with 1 to about 20 carbon atoms, alkenylor alkenyl halide groups with 1 to about 20 carbon atoms, aralkyl oraralkyl halide groups with 1 to about 20 carbon atoms, and the like,including substituted derivatives thereof.

In each occurrence, silicon groups are silicon-containing groups, whichinclude, but are not limited to, silyl groups such alkylsilyl groups,arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like,which in each occurrence have from 1 to about 20 carbon atoms. Forexample, silicon groups include trimethylsilyl and phenyloctylsilylgroups.

In each occurrence, boron groups are boron-containing groups, whichinclude, but are not limited to, —BR₂, —BX₂, —BRX, wherein X is amonoanionic group such as halide, hydride, alkoxide, alkyl thiolate, andthe like, and wherein R in each occurrence is alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylhaving from 1 to about 20 carbon atoms.

In another aspect of this invention, (X³) and (X⁴) are independentlyselected from an aliphatic group, a cyclic group, a combination of analiphatic group and a cyclic group, an amido group, a phosphido group,an alkyloxide group, an aryloxide group, an alkanesulfonate, anarenesulfonate, or a trialkylsilyl, or a substituted derivative thereof,any of which having from 1 to about 20 carbon atoms; or a halide. In yetanother aspect, (X³) and (X⁴) are independently: 1) F, Cl, Br, or I; 2)a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 3) ahydrocarbyloxide group, a hydrocarbylamino group, or atrihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A) is an alkyl group or an arylgroup, any of which having up to 12 carbon atoms. In still anotheraspect, (X³) and (X⁴) are independently selected from a hydrocarbylhaving from 1 to about 10 carbon atoms, or a halide. In another aspect,(X³) and (X⁴) are independently selected from fluoride, chloride,bromide, or iodide. In yet another aspect, (X³) and (X⁴) are chloride.In still another aspect, (X³) and (X⁴) are independently a hydrocarbylgroup having up to 20 carbon atoms, H, or BH₄.

In yet another aspect, the at least one first metallocene comprises acompound having the formula:

wherein

-   -   M^(1A) is zirconium or hafnium;    -   X^(3A) and X^(4A) are independently F, Cl, Br, I, benzyl,        phenyl, or methyl;    -   E^(A) is C or Si;    -   R^(1A) and R^(2A) are independently an alkyl group or an aryl        group, either of which having up to 12 carbon atoms, or        hydrogen, wherein at least one of R^(1A) or R^(2A) is an aryl        group;    -   R^(3A) and R^(4A) are independently a hydrocarbyl group or a        trihydrocarbylsilyl group, any of which having up to 20 carbon        atoms; or hydrogen;    -   n is an integer from 0 to 10, inclusive; and    -   R^(5A) and R^(6A) are independently a hydrocarbyl group having        up to 12 carbon atoms, or hydrogen.

In still another aspect, the at least one first metallocene comprises acompound having the formula:

wherein

-   -   M^(1B) is zirconium or hafnium;    -   R^(2B) is methyl or phenyl;    -   R^(3B) and R^(4B) are independently H or CH₃; and    -   n is an integer from 0 to 5, inclusive.

In a further aspect, the at least one first metallocene of thisinvention comprises a compound having the formula:

or any combination thereof.

In still another aspect, the at least one first metallocene of thisinvention can comprise, or can be selected from, any subset of the firstmetallocene formulas illustrated above. For example, the at least onefirst metallocene can comprise, or can be selected from,

or any combination thereof.

Numerous processes to prepare metallocene compounds that can be employedin this invention have been reported. For example, U.S. Pat. Nos.4,939,217, 5,191,132, 5,210,352, 5,347,026, 5,399,636, 5,401,817,5,420,320, 5,436,305, 5,451,649, 5,496,781, 5,498,581, 5,541,272,5,554,795, 5,563,284, 5,565,592, 5,571,880, 5,594,078, 5,631,203,5,631,335, 5,654,454, 5,668,230, 5,705,578, 5,705,579, 6,187,880, and6,509,427 describe such methods. Other processes to prepare metallocenecompounds that can be employed in this invention have been reported inreferences such as: Köppl, A. Alt, H. G. J. Mol. Catal A. 2001, 165, 23;Kajigaeshi, S.; Kadowaki, T.; Nishida, A.; Fujisaki, S. The ChemicalSociety of Japan, 1986, 59, 97; Alt, H. G.; Jung, M.; Kehr, G. J.Organomet. Chem. 1998, 562, 153-181; Alt, H. G.; Jung, M. J. Organomet.Chem. 1998, 568, 87-112; Jung, M., Doctoral Dissertation, University ofBayreuth, Bayreuth, Germany, 1997; Peifer, B., Doctoral Dissertation,University of Bayreuth, Bayreuth, Germany, 1995; and Zenk, R., DoctoralDissertation, University of Bayreuth, Bayreuth, Germany, 1994. Thefollowing treatises also describe such methods: Wailes, P. C.; Coutts,R. S. P.; Weigold, H. in Organometallic Chemistry of Titanium,Zirconium, and Hafnium, Academic; New York, 1974; Cardin, D. J.;Lappert, M. F.; and Raston, C. L.; Chemistry of Organo-Zirconium and-Hafnium Compounds; Halstead Press; New York, 1986.

The Second Metallocene Compound

According to one aspect of the present invention, the second metalloceneused to prepare the catalyst composition comprises unbridgedη⁵-cyclopentadienyl-type ligands selected from: 1) two independentlyselected, optionally substituted cyclopentadienyl ligands; 2) twoindependently selected, optionally substituted indenyl ligands; 3) onesubstituted cyclopentadienyl and one optionally substituted indenylligand; or 4) any combination thereof, as follows.

Thus, in one aspect of this invention, the at least one secondmetallocene comprises unbridged η⁵-cyclopentadienyl-type ligandsselected from two optionally substituted cyclopentadienyl ligands, twooptionally substituted indenyl ligands, or a combination thereof. Inthis aspect, the at least one second metallocene comprises an unbridgedmetallocene having the formula:(X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-A),wherein

M² is zirconium or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, asubstituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbylgroup having up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxidegroup, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any ofwhich having up to 20 carbon atoms; or 4) OBR^(B) ₂ or SO₃R^(B), whereinR^(B) is an alkyl group or an aryl group, any of which having up to 12carbon atoms; and

any substituent on the substituted cyclopentadienyl or substitutedindenyl is independently an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, an oxygen group, asulfur group, a nitrogen group, a phosphorus group, an arsenic group, acarbon group, a silicon group, or a boron group, any of which havingfrom 1 to 20 carbon atoms; a halide; or hydrogen.

In another aspect, the at least one second metallocene can comprise anunbridged metallocene having the formula:(X¹)(X⁶)(X⁷)(X⁸)M²  (M2-B),wherein

M² is zirconium or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, asubstituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently a hydrocarbyl group having up to 12carbon atoms, H, BH₄, or a halide; and

any substituent on the substituted cyclopentadienyl or substitutedindenyl is independently an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, any of which havingup to 20 carbon atoms;

In still another aspect, the at least one second metallocene cancomprise an unbridged metallocene having the formula:(X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-C),wherein

M² is zirconium or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, asubstituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbylgroup having up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxidegroup, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any ofwhich having up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), whereinR^(A) is an alkyl group or an aryl group, any of which having up to 12carbon atoms; wherein at least one (X⁷) and (X⁷) is a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; and

any substituent on the substituted cyclopentadienyl or substitutedindenyl is independently an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, an oxygen group, asulfur group, a nitrogen group, a phosphorus group, an arsenic group, acarbon group, a silicon group, or a boron group, any of which havingfrom 1 to 20 carbon atoms; a halide; or hydrogen.

In yet another aspect, the at least one second metallocene can comprisean unbridged metallocene having the formula:(X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-D),wherein

M² is zirconium or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, asubstituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently a hydrocarbyl group having up to 12carbon atoms, H, BH₄, or a halide, wherein at least one of (X⁷) and (X⁸)is a hydrocarbyl group, H, or BH₄; and

any substituent on the substituted cyclopentadienyl or substitutedindenyl is independently an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, any of which havingup to 20 carbon atoms.

Also in this aspect, the at least one second metallocene can alsocomprise an unbridged metallocene having the formula:

or a combination thereof, wherein

M^(2A) is, independently, zirconium or hafnium;

X^(7A) and X^(8A), in each occurrence, are independently F, Cl, Br, I,benzyl, phenyl, methyl; and

R^(7A) and R^(8A), in each occurrence, are independently H, methyl,ethyl, n-propyl, n-butyl, n-pentyl, CH₂CH₂CH₂Ph, CH₂CH═CH₂,CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂.

In another aspect, the at least one second metallocene can also comprisean unbridged metallocene having the formula:

or any combination thereof, wherein

M^(2B) is zirconium or hafnium;

X^(7B) and X^(8B) are independently benzyl, Cl, or methyl; and

R^(7B) and R^(8B) are independently H, methyl, ethyl, n-propyl, n-butyl,CH₂CH₂CH₂Ph, CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂.

Further, according to this aspect of the present invention, the at leastone second metallocene can comprise a compound having the formula:

or any combination thereof.

In yet another aspect, the at least one second metallocene can comprisea compound having the formula:

wherein

M^(2C) is zirconium or hafnium; and

X^(7C) and X^(8C) are independently benzyl, Cl, or methyl.

In still another aspect, the at least one second metallocene can beselected from

or a combination thereof.

In yet a further aspect of this invention, the at least one secondmetallocene can comprise unbridged η⁵-cyclopentadienyl-type ligandsselected from one substituted cyclopentadienyl and one optionallysubstituted indenyl ligand. In this aspect, the at least one secondmetallocene comprises an unbridged metallocene having the formula:(X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-A),wherein

M³ is zirconium or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms; (X¹⁰) is asubstituted indenyl group, wherein one substituent is an aliphaticgroup, an aromatic group, or a combination of aliphatic and cyclicgroups, any of which having up to 20 carbon atoms;

(X¹¹) and (X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbylgroup having up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxidegroup, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any ofwhich having up to 20 carbon atoms; or 4) OBR^(C) ₂ or SO₃R^(C), whereinR^(C) is an alkyl group or an aryl group, any of which having up to 12carbon atoms; and

any additional substituent on the substituted cyclopentadienyl orsubstituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 20 carbon atoms; a halide; or hydrogen.

In another aspect, the at least one second metallocene can comprise anunbridged metallocene having the formula:(X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-B),wherein

M³ is zirconium or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein any substituent isindependently a linear or branched alkyl group having up to 12 carbonatoms;

(X¹⁰) is a substituted indenyl group, wherein any substituent isindependently an aliphatic group, an aromatic group, or a combination ofaliphatic and cyclic groups, any of which having up to 20 carbon atoms;and

(X¹¹) and (X¹²) are independently a hydrocarbyl group having up to 12carbon atoms, H, BH₄, or a halide.

In still another aspect, the at least one second metallocene cancomprise an unbridged metallocene having the formula:(X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-C),wherein

M³ is zirconium or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms;

(X¹⁰) is a substituted indenyl group, wherein one substituent is analiphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms;

(X¹¹) and (X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbylgroup having up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxidegroup, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any ofwhich having up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), whereinR^(A) is an alkyl group or an aryl group, any of which having up to 12carbon atoms; wherein at least one (X¹¹) and (X¹²) is a hydrocarbylgroup having up to 20 carbon atoms, H, or BH₄; and

any additional substituent on the substituted cyclopentadienyl orsubstituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 20 carbon atoms; a halide; or hydrogen.

In yet another aspect, the at least one second metallocene can comprisean unbridged metallocene having the formula:(X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-D),wherein

M³ is zirconium or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein any substituent isindependently a linear or branched alkyl group having up to 12 carbonatoms;

(X¹⁰) is a substituted indenyl group, wherein any substituent isindependently an aliphatic group, an aromatic group, or a combination ofaliphatic and cyclic groups, any of which having up to 20 carbon atoms;and

(X¹¹) and (X¹²) are independently a hydrocarbyl group having up to 12carbon atoms, H, BH₄, or a halide, wherein at least one of (X⁷) and (X⁸)is a hydrocarbyl group, H, or BH₄.

Further to this aspect, the at least one second metallocene can alsocomprise any combination of metallocenes having the formulas(X⁵)(X⁶)(X⁷)(X⁸)M² and (X⁹)(X¹⁰)(X¹¹)(X¹²)M³, wherein the substituentsand the metals are defined above. That is, the at least one secondmetallocene can comprise any combination of (M2-A), (M2-B), (M2-C),(M2-D), (M3-A), (M3-B), (M3-C), (M3-D), or any combination thereof.

Also in this aspect, the at least one second metallocene can alsocomprise an unbridged metallocene having the formula:

wherein

M^(3A) is zirconium or hafnium;

R^(9A) is H or CH₃;

R^(10A) is H, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, orCH₂CH₂CH₂CH₃; and

X^(11A) and X^(12A) are independently F, Cl, Br, I, benzyl, phenyl, ormethyl.

In a further aspect of the invention, the at least one secondmetallocene can comprise a compound having the formula:

wherein

M^(3B) is zirconium or hafnium;

R^(9B) is H or CH₃; and

R^(10B) is H, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, or CH₂CH₂CH₂CH₃.

In still another aspect, the at least one second metallocene can beselected from

or any combination thereof.

In still another aspect, the at least one second metallocene of thisinvention can comprise, or can be selected from, any subset of thesecond metallocene formulas illustrated above. For example, the at leastone second metallocene can comprise, or can be selected from,

or any combination thereof.

In a further aspect, the metallocene component of this invention, thatis, the at least one first metallocene and the at least one secondmetallocene, can comprises any first metallocene or combination of firstmetallocenes having the formula (X¹)(X²)(X³)(X⁴)M¹, combined with anysecond metallocene or combination of second metallocenes having theformulas (X⁵)(X⁶)(X⁷)(X⁸)M² or (X⁹)(X¹⁰)(X¹¹)(X¹²)M³, wherein thesubstituents and the metals are defined herein. That is, the metallocenecomponent can comprise any first metallocene or combination of firstmetallocenes having the formulas (M1-A), (M2-B), or any combinationthereof, combined with any second metallocene or combination ofmetallocenes having the formula (M2-A), (M2-B), (M2-C), (M2-D), (M3-A),(M3-B), (M3-C), (M3-D), or any combination thereof. FIG. 1 illustratesthe formulas of some metallocenes that were used as disclosed in theExamples.

The Organoaluminum Compound

In one aspect, the present invention provides a catalyst compositioncomprising at least one first (ansa) metallocene compound, at least onesecond metallocene compound, at least one activator, and optionally atleast one co-catalyst such as an organoaluminum compound. Organoaluminumcompounds that can be used in this invention include, but are notlimited to compound with the formula:Al(X¹³)_(n)(X¹⁴)_(3-n),

wherein (X¹³) is a hydrocarbyl having from 1 to 20 carbon atoms; (X¹⁴)is an alkoxide or an aryloxide, any of which having from 1 to 20 carbonatoms, halide, or hydride; and n is a number from 1 to 3, inclusive. Inone aspect, (X¹³) is an alkyl having from 1 to about 10 carbon atoms.Examples of (X¹³) moieties include, but are not limited to, methyl,ethyl, propyl, butyl, hexyl, heptyl, octyl, and the like. In anotheraspect, examples of (X¹³) moieties include, but are not limited to,methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl,1-hexyl, 2-hexyl, 3-hexyl, isohexyl, heptyl, octyl, and the like. Inanother aspect, (X¹⁴) can be independently selected from fluoride,chloride, bromide, methoxide, ethoxide, or hydride. In yet anotheraspect, (X¹⁴) can be chloride.

In the formula Al(X¹³)_(n)(X¹⁴)_(3-n), n is a number from 1 to 3inclusive, and typically, n is 3. The value of n is not restricted to bean integer, therefore this formula includes sesquihalide compounds,other organoaluminum cluster compounds, and the like.

Generally, examples of organoaluminum compounds that can be used in thisinvention include, but are not limited to, trialkylaluminum compounds,dialkylaluminium halide compounds, dialkylaluminum alkoxide compounds,dialkylaluminum hydride compounds, and combinations thereof. Examples oforganoaluminum compounds that are useful in this invention include, butare not limited to trimethylaluminum, triethylaluminum,tripropylaluminum, tributylaluminum, tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), trihexylaluminum, triisohexylaluminum,trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride,diethylaluminum chloride, or any combination thereof. If the particularalkyl isomer is not specified, the compound is intended to encompass allisomers that can arise from a particular specified alkyl group. Thus, inanother aspect, examples of organoaluminum compounds that can be used inthis invention include, but are not limited to, trimethylaluminum,triethylaluminum, tripropylaluminum, tributylaluminum,triisobutylaluminum, trihexylaluminum, triisohexylaluminum,trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride,diethylaluminum chloride, or any combination thereof.

In one aspect, the present invention encompasses precontacting the atleast one first metallocene, precontacting the at least one secondmetallocene, or precontacting both the at least one first and the atleast one second metallocenes, and optionally an olefin monomer, andoptionally at least one organoaluminum co-catalyst, to form aprecontacted mixture, prior to contact this precontacted mixture withany activator, such as an activator-support, to form the activecatalyst. When the catalyst composition is prepared in this manner,typically, though not necessarily, a portion of the organoaluminumco-catalyst compound can be added to the precontacted mixture andanother portion of the organoaluminum compound can be added to thepostcontacted mixture prepared when the precontacted mixture iscontacted with the activator. However, all of the organoaluminumcompound can be used to prepare the catalyst in either the precontactingor postcontacting step. Alternatively, the catalyst components can becontacted in any order in multiple steps, or all the catalyst componentscan be contacted at substantially the same time in a single step.

Further, more than one organoaluminum compounds can be used, in eitherthe precontacting or the postcontacting step, or in any procedure inwhich the catalyst components are contacted. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed, regardless of whether a single organoaluminum compound isused, or more than one organoaluminum compound. In another aspect,typical organoaluminum compounds used in this invention include, but arenot limited to, triethylaluminum (TEA), tri-n-butylaluminum,triisobutylaluminum, or any combination thereof.

The Activator

In one aspect, the present invention encompasses a catalyst compositioncomprising at least one first metallocene compound as disclosed herein;at least one second metallocene as disclosed herein; optionally, atleast one organoaluminum compound; and at least one activator. Inanother aspect, the at least one activator can be an activator-support,selected from a solid oxide treated with an electron-withdrawing anion,a layered mineral, an ion-exchangeable activator-support, or anycombination thereof; an organoaluminoxane compound; an organoboroncompound; an organoborate compound; or any combination of any of theseactivators; each of which is provided herein.

Chemically-Treated Solid Oxide Activator-Supports

In one aspect, the present invention encompasses catalyst compositionscomprising an activator-support, which can be, or can comprise, achemically-treated solid oxide, and which is typically used incombination with an organoaluminum compound. In another aspect, theactivator-support comprises at least one solid oxide treated with atleast one electron-withdrawing anion; wherein the solid oxide can besilica, alumina, silica-alumina, aluminophosphate, aluminum phosphate,zinc aluminate, heteropolytungstates, titania, zirconia, magnesia,boria, zinc oxide, mixed oxides thereof, and the like, or any mixture orcombination thereof; and wherein the electron-withdrawing anion can befluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate,fluoroborate, fluorosulfate, trifluoroacetate, fluorophosphates,fluorozirconate, fluorosilicate, fluorotitanate, permanganate,substituted or unsubstituted alkanesulfonate, substituted orunsubstituted arenesulfonate, and the like, or any combination thereof.

The activator-support includes the contact product of at least one solidoxide compound and at least one electron-withdrawing anion source. Inone aspect, the solid oxide compound comprises an inorganic oxide. Thesolid oxide can be optionally calcined prior to contacting theelectron-withdrawing anion source. The contact product can also becalcined either during or after the solid oxide compound is contactedwith the electron-withdrawing anion source. In this aspect, the solidoxide compound can be calcined or uncalcined. In another aspect, theactivator-support can comprise the contact product of at least onecalcined solid oxide compound and at least one electron-withdrawinganion source.

In one aspect, the activator-support typically exhibits enhancedactivity as compared to the corresponding untreated solid oxidecompound. Thus, the activator-support can function as a catalystactivator as compared to the corresponding untreated solid oxide. Whilenot intending to be bound by theory, it is believed that theactivator-support can function as solid oxide supporting compound withan additional ionizing, polarizing, or bond weakening function,collectively termed an “activating” function, by weakening themetal-ligand bond between an anionic ligand and the metal in themetallocene. Thus, the activator-support is considered to exhibit an“activating” function, regardless of whether it is ionizes themetallocene, abstracts an anionic ligand to form an ion pair, weakensthe metal-ligand bond in the metallocene, simply coordinates to ananionic ligand when it contacts the activator-support, or any othermechanisms by which ionizing, polarizing, or bond weakening might occur.In preparing the metallocene-based catalyst composition of thisinvention, the activator-support is typically used along with acomponent that provides an activatable ligand such as an alkyl orhydride ligand to the metallocene, including but not limited to at leastone organoaluminum compound, when the metallocene compound does notalready comprise such a ligand.

In still another aspect, the activator-support of this inventioncomprises a solid inorganic oxide material, a mixed oxide material, or acombination of inorganic oxide materials, that is chemically-treatedwith an electron-withdrawing component, and optionally treated with atleast one other metal ion. Thus, the solid oxide of this inventionencompasses oxide materials such as alumina, “mixed oxide” compoundssuch as silica-alumina or silica-zirconia or silica-titania, andcombinations and mixtures thereof. The mixed metal oxide compounds suchas silica-alumina, with more than one metal combined with oxygen to forma solid oxide compound, can be made by co-gellation, impregnation orchemical deposition, and are encompassed by this invention.

In yet another aspect of this invention, the activator-support furthercomprises a metal or metal ion such as zinc, nickel, vanadium, silver,copper, gallium, tin, tungsten, molybdenum, or any combination thereof.Examples of activator-supports that further comprise a metal or metalion include, but are not limited to, zinc-impregnated chlorided alumina,zinc-impregnated fluorided alumina, zinc-impregnated chloridedsilica-alumina, zinc-impregnated fluorided silica-alumina,zinc-impregnated sulfated alumina, or any combination thereof.

In another aspect, the activator-support of this invention comprises asolid oxide of relatively high porosity, which exhibits Lewis acidic orBrønsted acidic behavior. The solid oxide is chemically-treated with anelectron-withdrawing component, typically an electron-withdrawing anion,to form a activator-support. While not intending to be bound by thefollowing statement, it is believed that treatment of the inorganicoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, the activator-support exhibits Lewis orBrønsted acidity which is typically greater than the Lewis or Brønstedacidity of the untreated solid oxide. One method to quantify the acidityof the chemically-treated and untreated solid oxide materials is bycomparing the polymerization activities of the treated and untreatedoxides under acid catalyzed reactions.

In one aspect, the chemically-treated solid oxide comprises a solidinorganic oxide comprising oxygen and at least one element selected fromGroup 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodictable, or comprising oxygen and at least one element selected from thelanthanide or actinide elements. (See: Hawley's Condensed ChemicalDictionary, 11^(th) Ed., John Wiley & Sons; 1995; Cotton, F. A.;Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced InorganicChemistry, 6^(th) Ed., Wiley-Interscience, 1999.) Usually, the inorganicoxide comprises oxygen and at least one element selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn or Zr.

Suitable examples of solid oxide materials or compounds that can be usedin the chemically-treated solid oxide of the present invention include,but are not limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO,Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO,ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixedoxides thereof, and combinations thereof. Examples of mixed oxides thatcan be used in the activator-support of the present invention include,but are not limited to, mixed oxides of any combination of Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, P, Sb, Si, Sn, Sr, Th, Ti,V, W, Y, Zn, Zr, and the like. Examples of mixed oxides that can be usedin the activator-support of the present invention also include, but arenot limited to, silica-alumina, silica-titania, silica-zirconia,zeolites, many clay minerals, pillared clays, alumina-titania,alumina-zirconia, aluminophosphate, and the like.

In a further aspect of this invention, the solid oxide material ischemically-treated by contacting it with at least oneelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material is optionallychemically-treated with at least one other metal ion, that can be thesame as or different from any metal element that constitutes the solidoxide material, then calcining to form a metal-containing ormetal-impregnated chemically-treated solid oxide. Alternatively, a solidoxide material and an electron-withdrawing anion source are contactedand calcined simultaneously. The method by which the oxide is contactedwith an electron-withdrawing component, typically a salt or an acid ofan electron-withdrawing anion, includes, but is not limited to, gelling,co-gelling, impregnation of one compound onto another, and the like.Typically, following any contacting method, the contacted mixture ofoxide compound, electron-withdrawing anion, and optionally the metal ionis calcined.

The electron-withdrawing component used to treat the oxide can be anycomponent that increases the Lewis or Brønsted acidity of the solidoxide upon treatment. In one aspect, the electron-withdrawing componentis typically an electron-withdrawing anion derived from a salt, an acid,or other compound such as a volatile organic compound that can serve asa source or precursor for that anion. Examples of electron-withdrawinganions include, but are not limited to, fluoride, chloride, bromide,iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate,fluorosulfate, trifluoroacetate, phosphate, fluorophosphate,fluorozirconate, fluorosilicate, fluorotitanate, permanganate,substituted or unsubstituted alkanesulfonate, substituted orunsubstituted arenesulfonate, and the like, including any mixtures andcombinations thereof. In addition, other ionic or non-ionic compoundsthat serve as sources for these electron-withdrawing anions can also beemployed in the present invention. In one aspect, the chemically-treatedsolid oxide comprises a sulfated solid oxide, and in another aspect, thechemically-treated oxide comprises sulfated alumina.

As used herein, the term alkanesulfonate refers to anions having thegeneral formula [R^(B)SO₂O]⁻, wherein R^(B) is a linear or branchedalkyl group having up to 20 carbon atoms, that is optionally substitutedwith at least one group selected independently from F, Cl, Br, I, OH,OMe, OEt, OCF₃, Ph, xylyl, mesityl, or OPh. Thus, the alkanesulfonatemay be referred to as a substituted or an unsubstituted alkanesulfonate.In one aspect, the alkyl group of the alkanesulfonate can have up to 12carbon atoms. In another aspect, the alkyl group of the alkanesulfonatecan have up to 8 carbon atoms, or up to 6 carbon atoms. In yet anotheraspect, examples of alkanesulfonates include, but are not limited to,methanesulfonate, ethanesulfonate, 1-propanesulfonate,2-propanesulfonate, 3-methylbutanesulfonate, trifluoromethane-sulfonate,trichloromethanesulfonate, chloromethanesulfonate,1-hydroxy-ethanesulfonate, 2-hydroxy-2-propanesulfonate,1-methoxy-2-propanesulfonate, and the like.

Also as used herein, the term arenesulfonate refers to anions having thegeneral formula [Ar^(A)SO₂O]⁻, wherein Ar^(A) is an aryl group having upto 14 carbon atoms, that is optionally substituted with at least onegroup selected independently from F, Cl, Br, I, Me, Et, Pr, Bu, OH, OMe,OEt, OPr, OBu, OCF₃, Ph, or OPh. Thus, the arenesulfonate may bereferred to as a substituted or an unsubstituted arenesulfonate. In oneaspect, the aryl group of the arenesulfonate can have up to 10 carbonatoms. In another aspect, the aryl group of the arenesulfonate can have6 carbon atoms. In yet another aspect, examples of arenesulfonatesinclude, but are not limited to, benzenesulfonate, naphthalenesulfonate,p-toluenesulfonate, m-toluenesulfonate, 3,5-xylenesulfonate,trifluoromethoxybenzenesulfonate, trichloromethoxybenzenesulfonate,trifluoromethylbenzenesulfonate, trichloromethylbenzenesulfonate,fluorobenzenesulfonate, chlorobenzenesulfonate,1-hydroxyethanebenzenesulfonate, 3-fluoro-4-methoxybenzenesulfonate, andthe like.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beany cation that allows the salt to revert or decompose back to the acidduring calcining. Factors that dictate the suitability of the particularsalt to serve as a source for the electron-withdrawing anion include,but are not limited to, the solubility of the salt in the desiredsolvent, the lack of adverse reactivity of the cation, ion-pairingeffects between the cation and anion, hygroscopic properties imparted tothe salt by the cation, and the like, and thermal stability of theanion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron withdrawing components can be contacted with the oxide materialsimultaneously or individually, and any order that affords the desiredactivator-support acidity. For example, one aspect of this invention isemploying two or more electron-withdrawing anion source compounds in twoor more separate contacting steps. Thus, one example of such a processby which an activator-support is prepared is as follows. A selectedsolid oxide compound, or combination of oxide compounds, is contactedwith a first electron-withdrawing anion source compound to form a firstmixture, this first mixture is then calcined, the calcined first mixtureis then contacted with a second electron-withdrawing anion sourcecompound to form a second mixture, followed by calcining said secondmixture to form a treated solid oxide compound. In such a process, thefirst and second electron-withdrawing anion source compounds aretypically different compounds, although they can be the same compound.

In one aspect of the invention, the solid oxide activator-support isproduced by a process comprising:

1) contacting a solid oxide compound with at least oneelectron-withdrawing anion source compound to form a first mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

In another aspect of this invention, the solid oxide activator-supportis produced by a process comprising:

1) contacting at least one solid oxide compound with a firstelectron-withdrawing anion source compound to form a first mixture; and

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support. Thus, the solid oxide activator-support is sometimesreferred to simply as a treated solid oxide compound.

Another aspect of this invention producing or forming the solid oxideactivator-support by contacting at least one solid oxide with at leastone electron-withdrawing anion source compound, wherein the at least onesolid oxide compound is calcined before, during or after contacting theelectron-withdrawing anion source, and wherein there is a substantialabsence of aluminoxanes and organoborates.

In one aspect of this invention, once the solid oxide has been treatedand dried, can be subsequently calcined. Calcining of the treated solidoxide is generally conducted in an ambient or inert atmosphere,typically in a dry ambient atmosphere, at a temperature from about 200°C. to about 900° C., and for a time of about 1 minute to about 100hours. In another aspect, calcining is conducted at a temperature fromabout 300° C. to about 800° C. and in another aspect, calcining isconducted at a temperature from about 400° C. to about 700° C. In yetanother aspect, calcining is conducted from about 1 hour to about 50hours, and in another aspect calcining is conducted, from about 3 hoursto about 20 hours. In still another aspect, calcining can be carried outfrom about 1 to about 10 hours at a temperature from about 350° C. toabout 550° C.

Further, any type of suitable ambient can be used during calcining.Generally, calcining is conducted in an oxidizing atmosphere, such asair. Alternatively, an inert atmosphere, such as nitrogen or argon, or areducing atmosphere such as hydrogen or carbon monoxide, can be used.

In another aspect of the invention, the solid oxide component used toprepare the chemically-treated solid oxide has a pore volume greaterthan about 0.1 cc/g. In another aspect, the solid oxide component has apore volume greater than about 0.5 cc/g, and in yet another aspect,greater than about 1.0 cc/g. In still another aspect, the solid oxidecomponent has a surface area from about 100 to about 1000 m²/g. Inanother aspect, solid oxide component has a surface area from about 200to about 800 m²/g, and in still another aspect, from about 250 to about600 m²/g.

The solid oxide material can be treated with a source of halide ion orsulfate ion, or a combination of anions, and optionally treated with atleast one metal ion, then calcined to provide the activator-support inthe form of a particulate solid. In one aspect, the solid oxide materialis treated with a source of sulfate, termed a sulfating agent, a sourceof chloride ion, termed a chloriding agent, a source of fluoride ion,termed a fluoriding agent, or a combination thereof, and calcined toprovide the solid oxide activator. In another aspect, useful acidicactivator-supports include, but are not limited to: bromided alumina;chlorided alumina; fluorided alumina; sulfated alumina; bromidedsilica-alumina, chlorided silica-alumina; fluorided silica-alumina;sulfated silica-alumina; bromided silica-zirconia, chloridedsilica-zirconia; fluorided silica-zirconia; sulfated silica-zirconia;chlorided zinc-alumina, triflate treated silica-alumina, a pillared claysuch as a pillared montmorillonite, optionally treated with fluoride,chloride, or sulfate; phosphated alumina, or other aluminophosphates,optionally treated with sulfate, fluoride, or chloride; or anycombination thereof. Further, any of the activator-supports canoptionally be treated with at least one other metal ion, typically froma metal salt or compound, wherein the metal ion can be the same as ordifferent from any metal that makes up the solid oxide material.

In one aspect of this invention, the treated oxide activator-supportcomprises a fluorided solid oxide in the form of a particulate solid,thus a source of fluoride ion is added to the oxide by treatment with afluoriding agent. In still another aspect, fluoride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent such asalcohol or water, including, but are not limited to, the one to threecarbon alcohols because of their volatility and low surface tension.Examples of fluoriding agents that can be used in this inventioninclude, but are not limited to, hydrofluoric acid (HF), ammoniumfluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumtetrafluoroborate (NH₄BF₄), ammonium silicofluoride (hexafluorosilicate)((NH₄)₂SiF₆), ammonium hexafluorophosphate (NH₄PF₆), tetrafluoroboricacid (HBF₄), ammonium hexafluorotitanate (NH₄)₂TiF₆, ammoniumhexafluorozirconate (NH₄)₂ZrF₆, analogs thereof, and combinationsthereof. For example, ammonium bifluoride NH₄HF₂ can be used as thefluoriding agent, due to its ease of use and ready availability.

In another aspect of the present invention, the solid oxide can betreated with a fluoriding agent during the calcining step. Anyfluoriding agent capable of thoroughly contacting the solid oxide duringthe calcining step can be used. For example, in addition to thosefluoriding agents described previously, volatile organic fluoridingagents can be used. Examples of volatile organic fluoriding agentsuseful in this aspect of the invention include, but are not limited to,freons, perfluorohexane, perfluorobenzene, fluoromethane,trifluoroethanol, and combinations thereof. Gaseous hydrogen fluoride orfluorine itself can also be used with the solid oxide is fluoridedduring calcining. One convenient method of contacting the solid oxidewith the fluoriding agent is to vaporize a fluoriding agent into a gasstream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid, thus a source of chloride ion is added to the oxideby treatment with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Inanother aspect of the present invention, the solid oxide can be treatedwith a chloriding agent during the calcining step. Any chloriding agentcapable of serving as a source of chloride and thoroughly contacting theoxide during the calcining step can be used. For example, volatileorganic chloriding agents can be used. Examples of volatile organicchloriding agents useful in this aspect of the invention include, butare not limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, orany combination thereof. Gaseous hydrogen chloride or chlorine itselfcan also be used with the solid oxide during calcining. One convenientmethod of contacting the oxide with the chloriding agent is to vaporizea chloriding agent into a gas stream used to fluidize the solid oxideduring calcination.

When the activator-support comprises a chemically-treated solid oxidecomprising a solid oxide treated with an electron-withdrawing anion, theelectron withdrawing anion can be typically added to the solid oxide inan amount greater than about 1% by weight of the solid oxide. In anotheraspect the electron withdrawing anion can be added to the solid oxide inan amount greater than about 2% by weight of the solid oxide, greaterthan about 3% by weight of the solid oxide, greater than about 5% byweight of the solid oxide, or greater than about 7% by weight of thesolid oxide.

In one aspect, the amount of electron-withdrawing ion, for examplefluoride or chloride ion, present before calcining the solid oxide isgenerally from about 2 to about 50% by weight, where the weight percentsare based on the weight of the solid oxide, for example silica-alumina,before calcining. In another aspect, the amount of electron-withdrawingion, for example fluoride or chloride ion, present before calcining thesolid oxide is from about 3 to about 25% by weight, and in anotheraspect, from about 4 to about 20% by weight. When halide ion is used asthe electron-withdrawing anion, it is used in an amount sufficient todeposit, after calcining, from about 0.1% to about 50% by weight halideion relative to the weight of the solid oxide. In another aspect, halideis used in an amount sufficient to deposit, after calcining, from about0.5% to about 40% by weight halide ion relative to the weight of thesolid oxide, or from about 1% to about 30% by weight halide ion relativeto the weight of the solid oxide. If the fluoride or chloride ion isadded during calcining, such as when calcined in the presence of CCl₄,there is typically no, or only trace levels, of fluoride or chloride ionin the solid oxide before calcining. Once impregnated with halide, thehalided oxide can be dried by any method known in the art including, butnot limited to, suction filtration followed by evaporation, drying undervacuum, spray drying, and the like, although it is also possible toinitiate the calcining step immediately without drying the impregnatedsolid oxide.

The silica-alumina used to prepare the treated silica-alumina can have apore volume greater than about 0.5 cc/g. In one aspect, the pore volumecan be greater than about 0.8 cc/g, and in another aspect, the porevolume can be greater than about 1.0 cc/g. Further, the silica-aluminacan have a surface area greater than about 100 m²/g. In one aspect, thesurface area is greater than about 250 m²/g, and in another aspect, thesurface area can be greater than about 350 m²/g. Generally, thesilica-alumina of this invention has an alumina content from about 5 toabout 95%. In one aspect, the alumina content of the silica-alumina canbe from about 5 to about 50%, and in another aspect, the alumina contentof the silica-alumina can be from about 8% to about 30% alumina byweight.

The sulfated solid oxide comprises sulfate and a solid oxide componentsuch as alumina or silica-alumina, in the form of a particulate solid.Optionally, the sulfated oxide is further treated with a metal ion suchthat the calcined sulfated oxide comprises a metal. In one aspect, thesulfated solid oxide comprises sulfate and alumina. In one aspect ofthis invention, the sulfated alumina is formed by a process wherein thealumina is treated with a sulfate source, including for example, but notlimited to, sulfuric acid or a sulfate salt such as ammonium sulfate,zinc sulfate, aluminum sulfate, nickel sulfate or copper sulfate. In oneaspect, this process can be performed by forming a slurry of the aluminain a suitable solvent such as alcohol or water, in which the desiredconcentration of the sulfating agent has been added. Suitable organicsolvents include, but are not limited to, the one to three carbonalcohols because of their volatility and low surface tension.

In this aspect, the amount of sulfate ion present before calcining isgenerally from about 1% to about 50% by weight, from about 2% to about30% by weight, of from about 5% to about 25% by weight, where the weightpercents are based on the weight of the solid oxide before calcining.Once impregnated with sulfate, the sulfated oxide can be dried by anymethod known in the art including, but not limited to, suctionfiltration followed by evaporation, drying under vacuum, spray drying,and the like, although it is also possible to initiate the calciningstep immediately.

In addition to being treated with an electron-withdrawing component suchas halide or sulfate ion, the solid inorganic oxide of this inventioncan optionally be treated with a metal source, including metal salts ormetal-containing compounds. In one aspect of the invention, thesecompounds can be added to or impregnated onto the solid oxide insolution form, and subsequently converted into the supported metal uponcalcining. Accordingly, the solid inorganic oxide can further comprise ametal selected from zinc, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, or a combination thereof. For example, zinccan be used to impregnate the solid oxide because it provides goodcatalyst activity and low cost. The solid oxide can be treated withmetal salts or metal-containing compounds before, after, or at the sametime that the solid oxide is treated with the electron-withdrawinganion.

Further, any method of impregnating the solid oxide material with ametal can be used. The method by which the oxide is contacted with ametal source, typically a salt or metal-containing compound, includes,but is not limited to, gelling, co-gelling, impregnation of one compoundonto another, and the like. Following any contacting method, thecontacted mixture of oxide compound, electron-withdrawing anion, and themetal ion is typically calcined. Alternatively, a solid oxide material,an electron-withdrawing anion source, and the metal salt ormetal-containing compound are contacted and calcined simultaneously.

In another aspect, the ansa-metallocene compound can be contacted withan olefin monomer and an organoaluminum cocatalyst for a first period oftime prior to contacting this mixture with the acidic activator-support.Once the precontacted mixture of metallocene, monomer, and componentthat provides an activatable ligand to the metallocene, including butnot limited to an organoaluminum cocatalyst, is contacted with theacidic activator-support, the composition further comprising the acidicactivator-support is termed the “postcontacted” mixture. Thepostcontacted mixture can be allowed to remain in further contact for asecond period of time prior to being charged into the reactor in whichthe polymerization process will be carried out.

Various processes to prepare solid oxide activator-supports that can beemployed in this invention have been reported. For example, U.S. Pat.Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594,6,376,415, 6,391,816, 6,395,666, 6,524,987, and 6,548,441, describe suchmethods, each of which is incorporated by reference herein, in itsentirety.

Ion-Exchangeable Activator-Supports and Layered MineralActivator-Supports

In one aspect of this invention, the activator-support used in preparingthe catalyst compositions of this invention can be, or can comprise, anion-exchangeable activator-support, including but not limited tosilicate and aluminosilicate compounds or minerals, either with layeredor non-layered structures, and any combination thereof. In anotheraspect of this invention, ion-exchangeable, layered aluminosilicatessuch as pillared clays can be used as activator-supports. When theactivator-support comprises an ion-exchangeable activator-support, itcan optionally be treated with at least one electron-withdrawing anionsuch as those disclosed herein, though typically the ion-exchangeableactivator-support is not treated with an electron-withdrawing anion.

In another aspect, the activator-support of this invention can be, orcan comprise, clay minerals having exchangeable cations and layerscapable of expanding. Typical clay mineral activator-supports include,but are not limited to, ion-exchangeable, layered aluminosilicates suchas pillared clays. Although the term “support” is used, it is not meantto be construed as an inert component of the catalyst composition, butrather is to be considered an active part of the catalyst composition,because of its intimate association with the ansa-metallocene and thecomponent that provides an activatable ligand to the metallocene, suchas an organoaluminum. While not intending to be bound by theory, it isbelieved that the ion exchangeable activator-support serves as aninsoluble reactant that reacts with the ansa-metallocene andorganoaluminum components to form a catalyst composition used to producepolymer.

In one aspect, the clay materials of this invention encompass materialseither in their natural state or that have been treated with variousions by wetting, ion exchange, or pillaring. Typically, the claymaterial activator-support of this invention comprises clays that havebeen ion exchanged with large cations, including polynuclear, highlycharged metal complex cations. However, the clay materialactivator-supports of this invention also encompass clays that have beenion exchanged with simple salts, including, but not limited to, salts ofAl(III), Fe(II), Fe(III) and Zn(II) with ligands such as halide,acetate, sulfate, nitrate, or nitrite.

In one aspect, the clay activator-support of this invention comprisespillared clays. The term pillared clays is used to refer to claymaterials that have been ion exchanged with large, typicallypolynuclear, highly charged metal complex cations. Examples of such ionsinclude, but are not limited to, Keggin ions which can have charges suchas 7+, various polyoxometallates, and other large ions. Thus, the termpillaring refers to a simple exchange reaction in which the exchangeablecations of a clay material are replaced with large, highly charged ions,such as Keggin ions. These polymeric cations are then immobilized withinthe interlayers of the clay and when calcined are converted to metaloxide “pillars,” effectively supporting the clay layers as column-likestructures. Thus, once the clay is dried and calcined to produce thesupporting pillars between clay layers, the expanded lattice structureis maintained and the porosity is enhanced. The resulting pores can varyin shape and size as a function of the pillaring material and the parentclay material used. Examples of pillaring and pillared clays are foundin: T. J. Pinnavaia, Science 220 (4595), 365-371 (1983); J. M. Thomas,Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3,pp. 55-99, Academic Press, Inc., (1972); U.S. Pat. Nos. 4,452,910;5,376,611; and 4,060,480; each of which is incorporated herein in itsentirety.

The pillaring process utilizes clay minerals having exchangeable cationsand layers capable of expanding. Any pillared clay that can enhance thepolymerization of olefins in the catalyst composition of the presentinvention can be used. Therefore, suitable clay minerals for pillaringinclude, but are not limited to: allophanes; smectites, bothdioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof suchas montmorillonites (bentonites), nontronites, hectorites, or laponites;halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layerclays; the fibrous clays including but not limited to sepiolites,attapulgites, and palygorskites; a serpentine clay; illite; laponite;saponite; or any combination thereof. In one aspect, the pillared clayactivator-support comprises bentonite or montmorillonite, noting thatthe principal component of bentonite is montmorillonite.

The pillared clay can be pretreated in the present invention. Forexample, in one embodiment, a pillared bentonite was pretreated bydrying at about 300° C. under an inert atmosphere, typically drynitrogen, for about 3 hours, before being added to the polymerizationreactor. This example of a pretreatment is not limiting, becausepreheating steps such as this many be carried out at many othertemperatures and times, including a combination of temperature and timesteps, all of which are encompassed by this invention.

The ion-exchangeable activator-supports such as pillared clays used toprepare the catalyst compositions of this invention can be combined withother inorganic support materials, including, but are not limited to,zeolites, inorganic oxides, phosphated inorganic oxides, and the like.In one aspect, typical support materials that can be used in this regardinclude, but are not limited to, silica, silica-alumina, alumina,titania, zirconia, magnesia, boria, fluorided alumina, silated alumina,thoria, aluminophosphate, aluminum phosphate, zinc aluminate, phosphatedsilica, phosphated alumina, silica-titania, coprecipitatedsilica/titania, fluorided/silated alumina, and any combination ormixture thereof.

The amount of ansa-metallocene compound in relation to theion-exchangeable activator-support used to prepare the catalystcomposition of this invention is typically from about 0.1 wt % to about15 wt % ansa-metallocene complex, based on the weight of theactivator-support component (not based on the final metallocene-claymixture). It was also found that from about 1 wt % to about 10 wt %ansa-metallocene works well to afford a catalyst that operates atdesired activities.

The mixture of ansa-metallocene and clay activator-support can becontacted and mixed for any length of time to allow thorough contactbetween the ansa-metallocene and activator-support. Sufficientdeposition of the metallocene component on the clay can be achievedwithout heating a mixture of clay and metallocene complex. For example,the ansa-metallocene compound and the clay material are simply mixedfrom about room temperature to about 200° F. in order to achieve thedeposition of the ansa-metallocene on the clay activator-support. Inanother aspect, the ansa-metallocene compound and the clay material aremixed from about 100° F. to about 180° F. in order to achieve thedeposition of the ansa-metallocene on the clay activator-support.

In another aspect, the present invention encompasses catalystcompositions comprising an acidic activator-support, which can comprisea layered mineral. The term “layered mineral” is used herein to describematerials such as clay minerals, pillared clays, ion-exchanged clays,exfoliated clays, exfoliated clays gelled into another oxide matrix,layered minerals mixed or diluted with other materials, and the like, orany combination thereof. When the acidic activator-support comprises alayered mineral, it can optionally be treated with at least oneelectron-withdrawing anion such as those disclosed herein, thoughtypically the layered mineral is not treated with anelectron-withdrawing anion. For example, at least one clay mineral canbe used as the activator-support.

Clay minerals generally include the large group of finely-crystalline,sheet-like layered minerals that are found in nature in fine-grainedsediments, sedimentary rocks, and the like, and which constitute a classof hydrous silicate and aluminosilicate minerals with sheet-likestructures and very high surface areas. This term is also used todescribe hydrous magnesium silicates with a phyllosilicate structure.Examples of clay minerals that can be used in this invention include,but are not limited to, allophanes; smectites, both dioctahedral (Al)and tri-octahedral (Mg) and derivatives thereof such as montmorillonites(bentonites), nontronites, hectorites, or laponites; halloysites;vermiculites; micas; fluoromicas; chlorites; mixed-layer clays; thefibrous clays including but not limited to sepiolites, attapulgites, andpalygorskites; a serpentine clay; illite; laponite; saponite; or anycombination thereof. Many common clay minerals belong to the kaolinite,montmorillonite, or illite groups of clays. Pillared clays can also beused as the activator-support of this invention, as disclosed herein.Pillared clays comprise clay minerals, typically of the of the smectitegroup and other phyllosilicates in addition to sepiolites andpalygorskites, that have been ion exchanged with large, typicallypolynuclear, highly charged metal complex cations.

In one aspect of this invention, when layered minerals are used asactivator-supports or metallocene activators, the layered minerals aretypically calcined prior to their use as activators. Typical calcinationtemperatures can range from about 100° C. to about 700° C., from about150° C. to about 500° C., or from about 200° C. to about 400° C.

Organoaluminoxane Activators

In one aspect, the present invention provides a catalyst compositioncomprising, or a catalyst composition comprising the contact product of,at least one first metallocene; at least one second metallocene;optionally, at least one organoaluminum compound; and at least oneactivator, wherein the activator can be selected independently from:

-   -   i) an activator-support selected from a solid oxide treated with        an electron-withdrawing anion, a layered mineral, an        ion-exchangeable activator-support, or any combination thereof;    -   ii) at least one organoaluminoxane compound;    -   iii) at least one organoboron or organoborate compound; or    -   iv) any combination thereof.

In another aspect, the present invention provides a catalyst compositioncomprising the contact product of at least one first metallocene; atleast one second metallocene; at least one organoaluminum compound; atleast one activator-support comprising a solid oxide treated with anelectron-withdrawing anion; and optionally, an aluminoxane cocatalyst.In still another aspect, the present invention provides a catalystcomposition comprising a first metallocene compound, a secondmetallocene compound, an aluminoxane cocatalyst, an optionalactivator-support, and an optional organoaluminum compound. However, inone aspect, the catalyst composition of this invention is substantiallyfree of aluminoxanes, and in another aspect, the catalyst composition ofthis invention has polymerization activity in the substantial absence ofaluminoxanes.

In another aspect, the present invention provides a catalyst compositioncomprising at least one first metallocene compound, at least one secondmetallocene compound, and an aluminoxane. In this aspect, the catalystcomposition is not required to comprise an activator-support and thecatalyst composition is also not required to comprise an organoaluminumcompound. Thus, any combination of first and second metallocenecompounds as disclosed herein can be combined with any of thealuminoxanes (poly(hydrocarbyl aluminum oxides)) disclosed herein, orany combination of aluminoxanes disclosed herein, to form a catalystcomposition of this invention. Further, any combination of first andsecond metallocene compounds disclosed herein can be combined with anyaluminoxane or combination of aluminoxanes, and optionally, a solidoxide treated with an electron-withdrawing anion; optionally, a layeredmineral; optionally, an ion-exchangeable activator-support; optionally,at least one organoboron compound; and optionally, at least oneorganoborate compound, to form a catalyst composition of this invention.

Aluminoxanes are also referred to as poly(hydrocarbyl aluminum oxides)or organoaluminoxanes. The other catalyst components are typicallycontacted with the aluminoxane in a saturated hydrocarbon compoundsolvent, though any solvent which is substantially inert to thereactants, intermediates, and products of the activation step can beused. The catalyst composition formed in this manner can be collected bymethods known to those of skill in the art, including but not limited tofiltration, or the catalyst composition can be introduced into thepolymerization reactor without being isolated.

In one aspect, the aluminoxane compound of this invention is anoligomeric aluminum compound, wherein the aluminoxane compound cancomprise linear structures, cyclic, or cage structures, or typicallymixtures of all three. Cyclic aluminoxane compounds having the formula:

whereinR is a linear or branched alkyl having from 1 to 10 carbon atoms, and nis an integer from 3 to about 10 are encompassed by this invention. The(AlRO)_(n) moiety shown here also constitutes the repeating unit in alinear aluminoxane. Thus, linear aluminoxanes having the formula:

whereinR is a linear or branched alkyl having from 1 to 10 carbon atoms, and nis an integer from 1 to about 50, are also encompassed by thisinvention.

Further, aluminoxanes can also have cage structures of the formula R^(t)_(5m+α)R^(b) _(m−α)Al_(4m)O_(3m), wherein m is 3 or 4 and αis=n_(Al(3))−n_(O(2))+n_(O(4)); wherein n_(Al(3)) is the number of threecoordinate aluminum atoms, n_(O(2)) is the number of two coordinateoxygen atoms, n_(O(4)) is the number of 4 coordinate oxygen atoms, R^(t)represents a terminal alkyl group, and R^(b) represents a bridging alkylgroup; wherein R is a linear or branched alkyl having from 1 to 10carbon atoms.

Thus, aluminoxanes can be represented generally by formulas such as(R—Al—O)_(n), R(R—Al—O)_(n)AlR₂, and the like, wherein the R group istypically a linear or branched C₁-C₆ alkyl such as methyl, ethyl,propyl, butyl, pentyl, or hexyl wherein n typically represents aninteger from 1 to about 50. In one embodiment, the aluminoxane compoundsof this invention include, but are not limited to, methylaluminoxane,ethylaluminoxane, n-propylaluminoxane, iso-propyl-aluminoxane,n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane,3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, orcombinations thereof.

While organoaluminoxanes with different types of R groups areencompassed by the present invention, methyl aluminoxane (MAO), ethylaluminoxane, or isobutyl aluminoxane are typical optional cocatalystsused in the catalyst compositions of this invention. These aluminoxanesare prepared from trimethylaluminum, triethylaluminum, ortriisobutylaluminum, respectively, and are sometimes referred to aspoly(methyl aluminum oxide), poly(ethyl aluminum oxide), andpoly(isobutyl aluminum oxide), respectively. It is also within the scopeof the invention to use an aluminoxane in combination with atrialkylaluminum, such as disclosed in U.S. Pat. No. 4,794,096.

The present invention contemplates many values of n in the aluminoxaneformulas (R—Al—O)_(n) and R(R—Al—O)_(n)AlR₂, and typically n is at leastabout 3. However, depending upon how the organoaluminoxane is prepared,stored, and used, the value of n can be variable within a single sampleof aluminoxane, and such a combination of organoaluminoxanes arecomprised in the methods and compositions of the present invention.

In preparing the catalyst composition of this invention comprising anoptional aluminoxane, the molar ratio of the aluminum in the aluminoxaneto the metallocene in the composition is usually from about 1:10 toabout 100,000:1. In one another aspect, the molar ratio of the aluminumin the aluminoxane to the metallocene in the composition is usually fromabout 5:1 to about 15,000:1. The amount of optional aluminoxane added toa polymerization zone is an amount within a range of about 0.01 mg/L toabout 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, or from about 1mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures which are wellknown in the art. Examples of organoaluminoxane preparations aredisclosed in U.S. Pat. Nos. 3,242,099 and 4,808,561. One example of howan aluminoxane can be prepared is as follows. Water, which is dissolvedin an inert organic solvent, can be reacted with an aluminum alkylcompound such as AlR₃ to form the desired organoaluminoxane compound.While not intending to be bound by this statement, it is believed thatthis synthetic method can afford a mixture of both linear and cyclic(R—Al—O)_(n) aluminoxane species, both of which are encompassed by thisinvention. Alternatively, organoaluminoxanes can be prepared by reactingan aluminum alkyl compound such as AlR₃ with a hydrated salt, such ashydrated copper sulfate, in an inert organic solvent.

Organoboron and Organoborate Activators

As provided herein, in one aspect, the present invention provides acatalyst composition comprising, or a catalyst composition comprisingthe contact product of, at least one first metallocene; at least onesecond metallocene; optionally, at least one organoaluminum compound;and at least one activator. The activator can be selected independentlyfrom: at least one activator-support as provided herein; at least oneorganoaluminoxane compound; at least one organoboron or organoboratecompound; or any combination thereof. Accordingly, in one aspect of thepresent invention the at least one activator can be selected from atleast one organoboron compound, at least one organoborate compound, or acombination thereof.

In a further aspect, the present invention provides a catalystcomposition comprising the contact product of at least one firstmetallocene; at least one second metallocene; at least oneorganoaluminum compound; at least one activator-support comprising asolid oxide treated with an electron-withdrawing anion; and optionally,an organoboron or organoborate cocatalyst. In another aspect, thepresent invention provides a catalyst composition comprising the contactproduct of: at least one first metallocene compound; at least one secondmetallocene; an organoboron or organoborate cocatalyst; anorganoaluminum compound; and optionally, an activator-support. In thisaspect, the catalyst composition is not required to comprise anactivator-support. Any ansa-metallocene compound disclosed herein can becombined with any of the organoboron or organoborate cocatalystsdisclosed herein, or any combination of organoboron or organoboratecocatalysts disclosed herein, along with a component that provides anactivatable ligand such as an alkyl or hydride ligand to themetallocene, when the metallocene compounds do not already comprise sucha ligand, such as an organoaluminum compound; to form a catalystcomposition. Further, any combination of first and second metallocenecompounds disclosed herein can be combined with any an organoboron ororganoborate cocatalyst; an organoaluminum compound; optionally, atleast one aluminoxane; and optionally, an activator-support; to form acatalyst composition of this invention. However, in one aspect, thecatalyst composition of this invention is substantially free oforganoboron or organoborate compounds, and in another aspect, thecatalyst composition of this invention have polymerization activity inthe substantial absence of organoboron or organoborate compounds.

In one aspect, as provided herein, the term “organoboron” compound canbe used to refer to neutral boron compounds, borate salts, orcombinations thereof. For example, the organoboron compounds of thisinvention can comprise a fluoroorgano boron compound, a fluoroorganoborate compound, or a combination thereof. Any fluoroorgano boron orfluoroorgano borate compound known in the art can be utilized. The termfluoroorgano boron compounds has its usual meaning to refer to neutralcompounds of the form BY₃. The term fluoroorgano borate compound alsohas its usual meaning to refer to the monoanionic salts of afluoroorgano boron compound of the form [cation]⁺[BY₄]⁻, where Yrepresents a fluorinated organic group. For convenience, fluoroorganoboron and fluoroorgano borate compounds are typically referred tocollectively by organoboron compounds, or by either name, as the contextrequires.

Examples of fluoroorgano borate compounds that can be used ascocatalysts in the present invention include, but are not limited to,fluorinated aryl borates such as, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, includingmixtures thereof. Examples of fluoroorgano boron compounds that can beused as cocatalysts in the present invention include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, includingmixtures thereof.

Although not intending to be bound by the following theory, theseexamples of fluoroorgano borate and fluoroorgano boron compounds, andrelated compounds, are thought to form “weakly-coordinating” anions whencombined with organometal compounds, as disclosed in U.S. Pat. No.5,919,983.

Generally, any amount of organoboron compound can be utilized in thisinvention. In one aspect, the molar ratio of the organoboron compound tothe metallocene compound in the composition is from about 0.1:1 to about10:1. Typically, the amount of the fluoroorgano boron or fluoroorganoborate compound used as a cocatalyst for the metallocene is in a rangeof from about 0.5 mole to about 10 moles of boron compound per mole ofmetallocene compound. In one aspect, the amount of fluoroorgano boron orfluoroorgano borate compound used as a cocatalyst for the metallocene isin a range of from about 0.8 mole to about 5 moles of boron compound permole of metallocene compound.

Non-Limiting Examples of the Catalyst Composition

Examples of the catalyst composition of this invention include, but arenot limited to the following. In one aspect or non-limiting example, thecatalyst composition can comprise, or the catalyst composition cancomprise the contact product of, at least one first metallocene, atleast one second metallocene, at least one organoaluminum compound, andat least one activator-support, wherein:

a) the at least one first metallocene comprises

or any combination thereof;

b) the at least one second metallocene comprises

or any combination thereof;

c) the at least one organoaluminum compound comprises triethylaluminum,tri-n-butylaluminum, triisobutylaluminum, or any combination thereof;and

d) the at least one activator-support comprises a sulfated solid oxide.

In another aspect or non-limiting example, the catalyst composition cancomprise, or the catalyst composition can comprise the contact productof, at least one first metallocene, at least one second metallocene, atleast one organoaluminum compound, and at least one activator-support,wherein:

a) the at least one first metallocene is selected from

or any combination thereof;

b) the at least one second metallocene is selected from

or any combination thereof;

c) the at least one organoaluminum compound comprises triethylaluminum,tri-n-butylaluminum, triisobutylaluminum, or any combination thereof;and

d) the at least one activator-support comprises a sulfated alumina.

In still another aspect or non-limiting example, the catalystcomposition can comprise, or the catalyst composition can comprise thecontact product of, at least one precontacted first metallocene, atleast one precontacted second metallocene, at least one precontactedorganoaluminum compound, at least one precontacted olefin, and at leastone postcontacted activator-support, wherein each of the firstmetallocene, the second metallocene, the organoaluminum compound, theolefin, and the activator-support are as disclosed herein.

The Optional Ionizing Ionic Compound Cocatalyst

In one aspect, the present invention provides a catalyst compositioncomprising, or a catalyst composition comprising the contact productof: 1) at least one first metallocene; 2) at least one secondmetallocene; 3) optionally, at least one organoaluminum compound; and 4)at least one activator, as disclosed herein. In another aspect, thepresent invention provides a catalyst composition as disclosed herein,comprising an optional ionizing ionic compound cocatalyst in addition tothese other components. However, in one aspect, the catalyst compositionof this invention is substantially free of ionizing ionic compounds, andin another aspect, the catalyst composition of this invention havepolymerization activity in the substantial absence of ionizing ioniccompounds. In still another aspect, the present invention provides acatalyst composition comprising at least one ansa-metallocene compoundas disclosed herein, at least one ionizing ionic compound cocatalyst,optionally at least one activator-support, and optionally at least oneorganoaluminum compound. Examples of ionizing ionic compound aredisclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938.

An ionizing ionic compound is an ionic compound which can function toenhance the activity of the catalyst composition. While not bound bytheory, it is believed that the ionizing ionic compound can be capableof reacting with the metallocene compound and converting the metalloceneinto a cationic metallocene compound. Again, while not intending to bebound by theory, it is believed that the ionizing ionic compound canfunction as an ionizing compound by completely or partially extractingan anionic ligand, possibly a non-η⁵-alkadienyl ligand such as (X³),(X⁴), (X⁷), (X⁸), (X¹¹), or (X¹²) from the first and/or secondmetallocenes. However, no aspect of the present invention depends on anytheory of action, regardless of whether the ionizing ionic compoundionizes the metallocene; abstracts an (X³), (X⁴), (X⁷), (X⁸), (X¹¹), or(X¹²) ligand in a fashion as to form an ion pair; weakens at least onemetal-(X³), metal-(X⁴), metal-(X⁷), metal-(X⁸), metal-(X¹¹), and/ormetal-(X¹²) bond in at least one first and/or second metallocene; simplycoordinates to at least one (X³), (X⁴), (X⁷), (X⁸), (X¹¹), or (X¹²)ligand; or any other mechanisms or combination of mechanisms by whichactivation can occur. Further, it is not necessary that the ionizingionic compound activate the metallocene only. The activation function ofthe ionizing ionic compound is evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositioncontaining catalyst composition that does not comprise any ionizingionic compound.

Examples of ionizing ionic compounds include, but are not limited to,the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl)-ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate,lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate,lithium tetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl)borate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate,triphenylcarbenium tetrakis(p-tolyl)aluminate, triphenylcarbeniumtetrakis(m-tolyl)aluminate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate, tropyliumtetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate,tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropyliumtetrakis(3,5-dimethylphenyl)aluminate, tropyliumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate,potassium tetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,triphenylcarbenium tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate,silver tetrakis(1,1,1,3,3,3-hexafluoroisopropanolato)aluminate, orsilver tetrakis(perfluoro-t-butoxy)aluminate, or any combinationthereof. However, these ionizing ionic compound are exemplary, and theionizing ionic compound is not limited thereto in the present invention.

The Olefin Monomer

In one aspect, the present invention encompasses a polymerizationcatalyst composition comprising, or a polymerization catalystcomposition comprising the contact product of, at least one firstmetallocene, at least one second metallocene, at least one activator,and optionally at least one co-catalyst, as disclosed herein.Unsaturated reactants that are useful in the polymerization processeswith catalyst compositions and processes of this invention includeolefin compounds having from 2 to about 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization reactions with at least onedifferent olefinic compound. In one aspect of a copolymerizationreaction of ethylene, copolymers of ethylene comprise a major amount ofethylene (>50 mole percent) and a minor amount of comonomer <50 molepercent), though this is not a requirement. The comonomers that can becopolymerized with ethylene should have from three to about 20 carbonatoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalysts of thisinvention include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, the five normal decenes, and mixturesof any two or more thereof. Cyclic and bicyclic olefins, including butnot limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene,and the like, can also be polymerized as described above.

In one aspect, when a copolymer is desired, the monomer ethylene can becopolymerized with a comonomer. In another aspect, examples of thecomonomer include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, or the five normal decenes. In anotheraspect, the comonomer can be 1-butene, 1-pentene, 1-hexene, 1-octene,1-decene, or styrene.

In one aspect, the amount of comonomer introduced into a reactor zone toproduce the copolymer is generally from about 0.01 to about 10 weightpercent comonomer based on the total weight of the monomer andcomonomer. In another aspect, the amount of comonomer introduced into areactor zone is from about 0.01 to about 5 weight percent comonomer, andin still another aspect, from about 0.1 to about 4 weight percentcomonomer based on the total weight of the monomer and comonomer.Alternatively, an amount sufficient to give the above describedconcentrations by weight, in the copolymer produced can be used.

While not intending to be bound by this theory, in the event thatbranched, substituted, or functionalized olefins are used as reactants,it is believed that steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. In one aspect, at least one reactant for the catalystcompositions of this invention is ethylene, so the polymerizations areeither homopolymerizations or copolymerizations with a differentacyclic, cyclic, terminal, internal, linear, branched, substituted, orunsubstituted olefin. In addition, the catalyst compositions of thisinvention can be used in polymerization of diolefin compounds, includingbut are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and1,5-hexadiene.

Preparation of the Catalyst Composition

In another aspect, this invention encompasses a catalyst composition anda method comprising contacting at least one first metallocene, at leastone second metallocene, at least one activator, and optionally at leastone co-catalyst, as disclosed herein. In one aspect of this invention,the at least one first metallocene, at least one second metallocene, ora combination of both first and second metallocene can be precontactedwith any other catalyst component, including, but not limited to, anolefinic monomer. In this aspect, the olefin monomer used in anyprecontacting steps is not necessarily the same olefin monomer to bepolymerized. Precontacting steps can include precontacting at least onefirst metallocene, at least one second metallocene, or a combinationthereof, with optionally at least one olefinic monomer, optionally atleast one organoaluminum cocatalyst, and optionally at least oneactivator such as a treated solid oxide activator-support for a firstperiod of time, prior to contacting the precontacted mixture with anyremaining catalyst composition components not employed in theprecontacting step. For example, the first period of time for contact,the precontact time, between a first metallocene, a second metallocene,an olefinic monomer, and an organoaluminum cocatalyst can typicallyrange from time about 1 minute to about 24 hours, and from about 0.1 toabout 1 hour is typical. Precontact times from about 10 minutes to about30 minutes are also typical.

In this aspect and example, once the precontacted mixture or more thanone precontacted mixture is contacted with the remaining catalystcomposition components, this composition is termed the postcontactedmixture. For example, a precontacted mixture of first and secondmetallocenes, olefin monomer, and organoaluminum cocatalyst canconstitute a precontacted mixture, which can subsequently be contactedwith a solid oxide activator, to form a postcontacted mixture.Typically, the postcontacted mixture can be allowed to remain in contactfor a second period of time, the postcontact time, prior to beinginitiating the polymerization process. In one aspect, postcontact timesbetween the treated solid oxide activator-support and the precontactedmixture typically range from time about 1 minute to about 24 hours, andfrom 0.1 to about 1 hour is typical. Postcontact times from about 10minutes to about 30 minutes are also typical.

In another aspect of this invention, any combination of various catalystcomponents can be contacted in the polymerization reactor simultaneouslywhile the polymerization reaction is proceeding. Alternatively, any twoor more of these catalyst components can be “precontacted” in a vesselor tube prior to their entering the reaction zone. This precontactingstep can be a continuous process, in which the precontacted product isfed continuously to the reactor, or it can be a stepwise or batchwiseprocess in which a batch of precontacted product can be added to make acatalyst composition. This precontacting step can be carried out over atime period that can range from a few seconds to as much as severaldays, or longer. In this aspect, the continuous precontacting step canlast typically from about 1 second to about 1 hour. Also in this aspect,the continuous precontacting step can last typically from about 10seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Alternatively the precontacting process can be carried out in multiplesteps, rather than a single step, in which multiple mixtures areprepared, each comprising a different set of catalyst components. Forexample, at least two catalyst components can be contacted forming afirst mixture, followed by contacting the first mixture with at leastone other catalyst component forming a second mixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (sequentially), in parallel, or a combination thereof. Forexample, a first mixture of two catalyst components can be formed in afirst vessel, a second mixture comprising the first mixture plus oneadditional catalyst component can be formed in the first vessel or in asecond vessel, which is typically placed downstream of the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component can be fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component can be fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or can be fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, a tube,a flask, a vessel of any type, or any combination thereof.

In one aspect, for example, a catalyst composition of this invention canbe prepared by contacting 1-hexene, triisobutylaluminum ortri-n-butylaluminum, and a first metallocene and a second metallocenefor at least about 30 minutes, followed by contacting this precontactedmixture with a sulfated alumina activator-support for at least about 10minutes up to one hour to form the active catalyst.

The precontacting step typically increases the productivity of thepolymer as compared to the same catalyst composition that is preparedwithout this precontacting step. The enhanced activity catalystcomposition of this invention can be used for homopolymerization of anα-olefin monomer such as ethylene or copolymerization of an α-olefin anda comonomer. However, neither a precontacting step nor a postcontactingstep is required for this invention.

The postcontacted mixture can be heated at a temperature and for aduration sufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the treated solid oxide activator-support, suchthat a portion of the components of the precontacted mixture isimmobilized, adsorbed, or deposited thereon. For example, thepostcontacted mixture can be heated from between about 0° F. to about150° F. Temperatures between about 40° F. to about 95° F. are typical ifthe mixture is heated at all.

In one aspect, the molar ratio of the combination of first and secondmetallocene compounds to the organoaluminum compound can be from about1:1 to about 1:10,000. In another aspect, the molar ratio of thecombination of first and second metallocene compounds to theorganoaluminum compound can be from about 1:1 to about 1:1,000, and inanother aspect, from about 1:1 to about 1:100. These molar ratiosreflect the ratio of the combined first and second metallocene compoundsto the total amount of organoaluminum compound in both the precontactedmixture and the postcontacted mixture combined.

When a precontacting step is used, generally, the molar ratio of olefinmonomer to the combined first and second metallocene compounds in theprecontacted mixture can be from about 1:10 to about 100,000:1, or fromabout 10:1 to about 1,000:1.

In another aspect of this invention, the weight ratio of the solid oxideactivator to the organoaluminum compound can range from about 1:5 toabout 1,000:1. In another aspect, the weight ratio of the solid oxideactivator to the organoaluminum compound can be from about 1:3 to about100:1, and in yet another aspect, from about 1:1 to about 50:1.

In a further aspect of this invention, the weight ratio of thecombination of first and second metallocenes to treated solid oxideactivator-support can be from about 1:1 to about 1:1,000,000. Yetanother aspect of this invention is the weight ratio of the combinedfirst and second metallocenes to treated solid oxide activator-supportwhich can be from about 1:10 to about 1:100,000, and in another aspect,from about 1:20 to about 1:1000.

One aspect of this invention is that aluminoxane is not required to formthe catalyst composition disclosed herein, a feature that allows lowerpolymer production costs. Accordingly, in one aspect, the presentinvention can use AlR₃-type organoaluminum compounds and a treated solidoxide activator-support in the absence of aluminoxanes. Additionally, noexpensive borate compounds or MgCl₂ are required to form the catalystcomposition of this invention, although aluminoxane, borate compounds,MgCl₂, or any combination thereof can optionally be used in the catalystcomposition of this invention. Further, in one aspect, cocatalysts suchas aluminoxanes, organoboron compounds, ionizing ionic compounds, or anycombination thereof can be used as cocatalysts with a first metallocene,a second metallocene, an activator-support, and an organoaluminumcompound. However, the catalyst compositions of the present inventionare active in the substantial absence of cocatalysts such asaluminoxanes, organoboron compounds, ionizing ionic compounds, or anycombination thereof.

Thus, in one aspect, this invention provides a process to produce acatalyst composition, comprising contacting at least one firstmetallocene, at least one second metallocene, and at least oneco-catalyst, wherein the at least one first metallocene, at least onesecond metallocene, and at least one co-catalyst are disclosed herein.In this aspect, the at least one cocatalyst can comprise at least oneorganoaluminum compound and at least one activator-support, as describedherein.

According to another aspect, the present invention provides a process toproduce a catalyst composition, comprising

-   -   contacting at least one first metallocene, at least one second        metallocene, optionally, at least one olefin, and at least one        organoaluminum compound for a first period of time to form a        precontacted mixture comprising at least one precontacted first        metallocene, at least one precontacted second metallocene, at        least one precontacted organoaluminum compound, and optionally,        at least one precontacted olefin; and    -   contacting the precontacted mixture with at least one        activator-support and optionally additional organoaluminum        compound for a second period of time to form a postcontacted        mixture comprising at least one postcontacted first metallocene,        at least one postcontacted second metallocene, at least one        postcontacted organoaluminum compound, optionally, at least one        postcontacted olefin, and at least one postcontacted        activator-support.

In one aspect, the catalytic activity of the catalyst of this inventionis typically greater than or equal to about 100 grams polyethylene pergram of chemically treated solid oxide per hour (abbreviatedgP/(gCTSO·hr)). In another aspect, the catalyst of this invention can becharacterized by an activity of greater than or equal to about 250gP/(gCTSO·hr), and in another aspect, an activity of greater than orequal to about 500 gP/(gCTSO·hr). In still another aspect, the catalystof this invention can be characterized by an activity of greater than orequal to about 1000 gP/(gCTSO·hr), and in another aspect, an activity ofgreater than or equal to about 2000 gP/(gCTSO·hr). This activity ismeasured under slurry polymerization conditions, using isobutane as thediluent, and with a polymerization temperature from about 75° C. toabout 100° C., and an ethylene concentration from about 5 mole % toabout 20 mol %. In one aspect, this activity is measured under slurrypolymerization conditions, using isobutane as the diluent, and with apolymerization temperature of about 90° C., and an ethylene pressure ofabout 550 psig. The reactor should have substantially no indication ofany wall scale, coating or other forms of fouling upon making thesemeasurements.

Utility of the Catalyst Composition in Polymerization Processes

The catalysts of the present invention are intended for any olefinpolymerization method known in the art, using various types ofpolymerization reactors. As used herein, “polymerization reactor”includes any polymerization reactor capable of polymerizing olefinmonomers to produce homopolymers or copolymers. Such homopolymers andcopolymers are referred to as resins or polymers. The various types ofreactors include those that may be referred to as batch, slurry,gas-phase, solution, high pressure, tubular or autoclave reactors. Gasphase reactors may comprise fluidized bed reactors or staged horizontalreactors. Slurry reactors may comprise vertical or horizontal loops.High pressure reactors may comprise autoclave or tubular reactors.Reactor types can include batch or continuous processes. Continuousprocesses could use intermittent or continuous product discharge.Processes may also include partial or full direct recycle of un-reactedmonomer, un-reacted comonomer, and/or diluent.

Polymerization reactor systems of the present invention may comprise onetype of reactor in a system or multiple reactors of the same ordifferent type. Production of polymers in multiple reactors may includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorsmay be different from the operating conditions of the other reactors.Alternatively, polymerization in multiple reactors may include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems may include anycombination including, but not limited to, multiple loop reactors,multiple gas reactors, a combination of loop and gas reactors, multiplehigh pressure reactors or a combination of high pressure with loopand/or gas reactors. The multiple reactors may be operated in series orin parallel.

According to one aspect of the invention, the polymerization reactorsystem may comprise at least one loop slurry reactor. Such reactors areknown in the art and may comprise vertical or horizontal loops. Monomer,diluent, catalyst and optionally any comonomer may be continuously fedto a loop reactor where polymerization occurs. Generally, continuousprocesses may comprise the continuous introduction of a monomer, acatalyst, and a diluent into a polymerization reactor and the continuousremoval from this reactor of a suspension comprising polymer particlesand the diluent. Reactor effluent may be flashed to remove the solidpolymer from the liquids that comprise the diluent, monomer and/orcomonomer. Various technologies may be used for this separation stepincluding but not limited to, flashing that may include any combinationof heat addition and pressure reduction; separation by cyclonic actionin either a cyclone or hydrocyclone; or separation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess), which is well known in the art is disclosed, for example, inU.S. Pat. Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235,6,262,191 and 6,833,415, each of which is incorporated by reference inits entirety herein.

Suitable diluents used in slurry polymerization are well known in theart and include, but are not limited to, the monomer being polymerizedand hydrocarbons that are liquids under reaction conditions. Examples ofsuitable diluents include, but are not limited to, hydrocarbons such aspropane, cyclohexane, isobutane, n-butane, n-pentane, isopentane,neopentane, and n-hexane. Some loop polymerization reactions can occurunder bulk conditions where no diluent is used. An example ispolymerization of propylene monomer as disclosed in U.S. Pat. No.5,455,314, which is incorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor may comprise at least one gas phase reactor. Such systems areknown in the art and may employ a continuous recycle stream containingone or more monomers continuously cycled through a fluidized bed in thepresence of the catalyst under polymerization conditions. A recyclestream may be withdrawn from the fluidized bed and recycled back intothe reactor. Simultaneously, polymer product may be withdrawn from thereactor and new or fresh monomer may be added to replace the polymerizedmonomer. Such gas phase reactors may comprise a process for multi-stepgas-phase polymerization of olefins, in which olefins are polymerized inthe gaseous phase in at least two independent gas-phase polymerizationzones while feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790 and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor may comprise a tubular reactor or an autoclavereactor, both of which are known in the art. Tubular reactors may haveseveral zones where fresh monomer, initiators, or catalysts are added.Monomer may be entrained in an inert gaseous stream and introduced atone zone of the reactor. Initiators, catalysts, and/or catalystcomponents may be entrained in a gaseous stream and introduced atanother zone of the reactor. The gas streams may be intermixed forpolymerization. Heat and pressure may be employed appropriately toobtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor may comprise a solution polymerization reactor wherein themonomer is contacted with the catalyst composition by suitable stirringor other means. A carrier comprising an inert organic diluent or excessmonomer may be employed. If desired, the monomer may be brought in thevapor phase into contact with the catalytic reaction product, in thepresence or absence of liquid material. The polymerization zone ismaintained at temperatures and pressures that will result in theformation of a solution of the polymer in a reaction medium. Agitationmay be employed to obtain better temperature control and to maintainuniform polymerization mixtures throughout the polymerization zone.Adequate means are utilized for dissipating the exothermic heat ofpolymerization. These reactors are known in the art.

Polymerization reactors suitable for the present invention may furthercomprise any combination of at least one raw material feed system, atleast one feed system for catalyst or catalyst components, and/or atleast one polymer recovery system. Suitable reactor systems for thepresent invention may further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, load out,laboratory analysis, and process control.

Conditions that are controlled for polymerization efficiency and toprovide resin properties include temperature, pressure and theconcentrations of various reactants. Polymerization temperature canaffect catalyst productivity, polymer molecular weight and molecularweight distribution. Suitable polymerization temperature may be anytemperature below the de-polymerization temperature according to theGibbs Free energy equation. Typically this includes from about 60° C. toabout 280° C., for example, and from about 70° C. to about 110° C.,depending upon the type of polymerization reactor.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than about 1000 psig. Pressure for gasphase polymerization is usually from about 200 to about 500 psig. Highpressure polymerization in tubular or autoclave reactors is generallyrun at from about 20,000 to about 75,000 psig. Polymerization reactorscan also be operated in a supercritical region occurring at generallyhigher temperatures and pressures. Operation above the critical point ofa pressure/temperature diagram (supercritical phase) may offeradvantages.

The concentration of various reactants can be controlled to produceresins with certain physical and mechanical properties. The proposedend-use product that will be formed by the resin and the method offorming that product determines the desired resin properties. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxationand hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching and rheologicalmeasurements.

The concentrations of monomer, co-monomer, hydrogen, co-catalyst,modifiers, and electron donors are important in producing these resinproperties. Comonomer is used to control product density. Hydrogen isused to control product molecular weight. Co-catalysts can be used toalkylate, scavenge poisons and control molecular weight. Modifiers canbe used to control product properties and electron donors affectstereoregularity. In addition, the concentration of poisons must beminimized since they impact the reactions and product properties.

The polymer or resin may be formed into various articles, including, butnot limited to, bottles, drums, toys, household containers, utensils,film products, drums, fuel tanks, pipes, geomembranes, and liners.Various processes may be used to form these articles, including, but notlimited to, blow molding, extrusion molding, rotational molding,thermoforming, cast molding and the like. After polymerization,additives and modifiers can be added to the polymer to provide betterprocessing during manufacturing and for desired properties in the endproduct. Additives include surface modifiers such as slip agents,antiblocks, tackifiers; antioxidants such as primary and secondaryantioxidants; pigments; processing aids such as waxes/oils andfluoroelastomers; and special additives such as fire retardants,antistats, scavengers, absorbers, odor enhancers, and degradationagents.

Ethylene Polymers Prepared According to this Invention

In one aspect, the ethylene polymers and copolymers produced using thecatalyst composition of this invention can be characterized by a bimodalor multimodal molecular weight distribution, examples of which areillustrated in FIGS. 2 and 3. The high molecular weight component isobserved to be formed with the first, or ansa-metallocene component,while the low molecular weight component is observed to be formed withsecond metallocene component. Regarding the high molecular weightcomponent, lower than expected levels of long chain branching (LCB) areobserved, typically, as compared to polymers produced usingansa-metallocenes without an olefin-containing moiety bonded to acyclopentadienyl-type ligand, even when the comparative metallocenecomprises at least one aryl group bonded to the bridging atom of thebridging ligand. In a further aspect, the high molecular weight polymeris characterized typically by higher molecular weights than are usuallyobserved when using a tightly-bridged ansa-metallocene compound withoutat least one aryl group bonded to the bridging atom of the bridgingligand, even when the comparative metallocene comprises anolefin-containing moiety bonded to a cyclopentadienyl-type ligand.

FIG. 2 provides comparison gel permeation chromatograms (GPCs) forethylene homopolymers and copolymers of Examples 1-6 (E1-E6), preparedas provided in Table 1, and FIG. 3 provides comparison gel permeationchromatograms (GPCs) for ethylene copolymers prepared according toExamples 7-13 (E7-E13), prepared as provided in Table 2. The bimodalmolecular weight distribution as evident in these chromatograms isuseful for pipe and film applications. As illustrated by these FIGURES,the resins produced by the inventive catalysts are observed to havebroad molecular weight distributions. Another indication of thismolecular weight distribution is the large values of M_(w)/M_(n), asprovided in Tables 1 and 2. The low molecular weight components, as seenin the low molecular weight GPC peak of FIGS. 2 and 3, are sufficientlylow in molecular weight to provide good melt flow without the presenceof very low molecular weight tails, a feature which can contribute tosmoking during processing. Further, the high molecular weightcomponents, indicated by M_(w) and M_(z) of Tables 1 and 2, aresufficient to provide high physical strength to the final products.

DEFINITIONS

In order to more clearly define the terms used herein, the followingdefinitions are provided. To the extent that any definition or usageprovided by any document incorporated herein by reference conflicts withthe definition or usage provided herein, the definition or usageprovided herein controls.

The term “polymer” is used herein to mean homopolymers comprisingethylene and/or copolymers of ethylene and another olefinic comonomer.“Polymer” is also used herein to mean homopolymers and copolymers of anyother polymerizable monomer disclosed herein.

The term “cocatalyst” is generally used herein to refer to theorganoaluminum compounds that can constitute one component of thecatalyst composition, but also refers to the optional components of thecatalyst composition including, but not limited to, aluminoxanes,organoboron compounds, organoborate compounds, or ionizing ioniccompounds, as disclosed herein. In one aspect, cocatalysts can beorganoaluminum compounds of the formula Al(X¹³)_(n)(X¹⁴)_(3-n), wherein(X¹³) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X¹⁴) isalkoxide or aryloxide, any of which having from 1 to about 20 carbonatoms, halide, or hydride; and n is a number from 1 to 3, inclusive. Theterm cocatalyst can be used regardless of the actual function of thecompound or any chemical mechanism by which the compound might operate.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Typically, the precontacted mixture describes a mixtureof at least one metallocene, optionally at least one olefin monomer, andat least one organoaluminum compound, before this mixture is contactedwith the activator-support and optionally additional organoaluminumcompound. Thus, “precontacted” describes components that are used tocontact each other, but prior to contacting the components in thesecond, postcontacted mixture. Accordingly, this invention mayoccasionally distinguish between a component used to prepare theprecontacted mixture and that component after the mixture has beenprepared. For example, according to this description, it is possible forthe precontacted organoaluminum compound, once it is contacted with themetallocene and the optional olefin monomer, to have reacted to form atleast one different chemical compound, formulation, or structure fromthe distinct organoaluminum compound used to prepare the precontactedmixture. In this case, the precontacted organoaluminum compound orcomponent is described as comprising an organoaluminum compound that wasused to prepare the precontacted mixture.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of metallocene, olefin monomer,organoaluminum compound, and activator-support, formed from contactingthe precontacted mixture of a portion of these components with the anyadditional components added to make up the postcontacted mixture.Generally, the additional component added to make up the postcontactedmixture is the solid oxide activator, and optionally can include anorganoaluminum compound the same or different from the organoaluminumcompound used to prepare the precontacted mixture, as described herein.Accordingly, this invention may also occasionally distinguish between acomponent used to prepare the postcontacted mixture and that componentafter the mixture has been prepared.

The term tightly-bridged ansa-metallocene describes a metallocenecompound in which the two η⁵-cycloalkadienyl-type ligands in themolecule are linked by a bridging moiety, wherein the shortest linkbetween the two η⁵-cycloalkadienyl-type ligands comprises one atom.Thus, the length of the bridge or the chain between the twocyclopentadienyl-type ligands is a single atom, although this bridgingatom is substituted. Thus, the metallocenes of this invention arebridged bis(η⁵-cycloalkadienyl)-type compounds, wherein theη⁵-cycloalkadienyl portions include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including substituted analogsand partially saturated analogs thereof. Possible substituents on theseligands include hydrogen, therefore the description “substitutedderivatives thereof” in this invention includes partially saturatedligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene is referred to simply as the “catalyst”, in much the sameway the term “cocatalyst” is used herein to refer to the organoaluminumcompound.

The terms “catalyst composition,” “catalyst mixture,” and the like donot depend upon the actual product of the reaction of the components ofthe mixtures, the nature of the active catalytic site, or the fate ofthe aluminum cocatalyst, ansa-metallocene, any olefin monomer used toprepare a precontacted mixture, or the solid oxide activator aftercombining these components. Therefore, the terms catalyst composition,catalyst mixture, and the like include both heterogeneous compositionsand homogenous compositions.

The term “hydrocarbyl” is used to specify a hydrocarbon radical groupthat includes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl,cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl,and the like, and includes all substituted, unsubstituted, branched,linear, heteroatom substituted derivatives thereof. Unless otherwisespecified, the hydrocarbyl groups of this invention typically compriseup to about 20 carbon atoms. In one aspect, hydrocarbyl groups can haveup to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.

The term “hydrocarbyloxide” group is used generically to refercollectively to both alkoxide and aryloxide groups. Unless otherwisespecified, the hydrocarbyl oxide groups of this invention typicallycomprise up to about 20 carbon atoms. In one aspect, hydrocarbyloxidegroups can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6carbon atoms.

The term “hydrocarbylamino” group is used generically to refercollectively to alkylamino (NHR), arylamino (NHAr), dialkylamino (NR₂),and diarylamino (NAr₂) groups. Unless otherwise specified, thehydrocarbyl amino groups of this invention typically comprise up toabout 20 carbon atoms. In one aspect, hydrocarbylamino groups can haveup to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.

The term “alkenyl” is used broadly to specify a hydrocarbyl group thatcomprises an alkene moiety, regardless of the particular regiochemistryof the alkene moiety and encompassing all stereochemical isomers. Thus,for example, the term alkenyl is intended to include anyCH═CH₂-substituted or CH═CMe₂-substituted alkyl group, regardless ofwhere the substitution occurs within the alkyl group. Terms such asolefin-containing hydrocarbyl group or olefin-containing pendant groupare typically used interchangeably with alkenyl group, againillustrating that these terms are not intended to be bound by theparticular location of the C═C double bond within the group. Unlessotherwise specified, the alkenyl groups of this invention typicallycomprise up to about 20 carbon atoms. In one aspect, alkenyl groups canhave up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbonatoms.

The terms solid oxide activator-support, acidic activator-support,activator-support, treated solid oxide, treated solid oxideactivator-support, treated solid oxide compound, and the like are usedherein to indicate a treated, solid, inorganic oxide of relatively highporosity, which exhibits Lewis acidic or Brønsted acidic behavior, whichhas been treated with an electron-withdrawing component, typically ananion, and which is calcined. The electron-withdrawing component istypically an electron-withdrawing anion source compound. Thus, thetreated solid oxide compound comprises the calcined contact product ofat least one solid oxide compound with at least one electron-withdrawinganion source compound. Typically, the activator-support or “treatedsolid oxide compound” comprises at least one ionizing, acidic solidoxide compound. The terms support or activator-support are not used toimply these components are inert, and this component should not beconstrued as an inert component of the catalyst composition.

The term “activator,” as used herein, refers generally to a substancethat is capable of converting the contact product of: 1) a metallocenecomponent; and 2) a component that provides an activatable ligand suchas an alkyl or hydride ligand to the metallocene, when the metallocenecompound does not already comprise such a ligand; into a catalyst thatcan polymerize olefins. This term is used regardless of whether anactivator ionizes the metallocene, abstracts an anionic ligand to forman ion pair, weakens a metal-ligand bond in the metallocene, simplycoordinates to an anionic ligand, or any other mechanism. As disclosedherein, the contact product comprises at least one activator, which canbe selected independently from: i) an activator-support selected from asolid oxide treated with an electron-withdrawing anion, a layeredmineral, an ion-exchangeable activator-support, or any combinationthereof; ii) an organoaluminoxane compound; iii) an organoboron or anorganoborate compound; or iv) any combination of these components.

The term “clay” is used herein to refer to that component of thecatalyst composition, a substantial portion of which constitutes a claymineral or a mixture of clay minerals that have been pretreated byeither exchanging cations, pillaring or simply wetting, that can be usedas an activator-support in the catalyst composition described herein.The transition metal compound and organometal cocatalyst are reactedwith the clay activator-support to form the active catalyst. While notintending to be bound by the following statement, the clay component ofthe catalyst composition of this invention probably functions as anactivator-support for the transition metal compound, as well as acocatalyst from the standpoint that it is in intimate physical chemicalcontact with the transition metal component.

As used herein, the collective term “clay mineral” is used herein todescribe the large group of finely-crystalline, sheet like clay mineralsthat are found in nature in fine-grained sediments, sedimentary rocks,and the like. Clay minerals are a class of hydrous silicate andaluminosilicate minerals with sheet-like structures and very highsurface areas. This term is also used to describe hydrous magnesiumsilicates with a phyllosilicate structure. Many common clay mineralsbelong to the kaolinite, montmorillonite, or illite groups of clays.Thus, the term “clay mineral” is not used herein to refer to thefine-grained soil consisting of mineral particles, not necessarily clayminerals, that are less than about 0.002 mm in size.

The term “pillared clay” is used herein to refer to a component of thecatalyst composition comprising clay minerals, typically of the of thesmectite group and other phyllosilicates in addition to sepiolites andpalygorskites, that have been ion exchanged with large, typicallypolynuclear, highly charged metal complex cations. Examples of such ionsinclude, but are not limited to, Keggin ions which can have charges suchas 7+, various polyoxometallates, and other large ions. Thus, the termpillaring refers to a simple exchange reaction in which the exchangeablecations of a clay material are replaced with large, highly charged ions,such as Keggin ions. These polymeric cations are then immobilized withinthe interlayers of the clay and when calcined are converted to metaloxide “pillars,” effectively supporting the clay layers as column-likestructures. Examples of pillaring and pillared clays are found in: T. J.Pinnavaia, Science 220 (4595), 365-371 (1983); J. M. Thomas,Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3,pp. 55-99, Academic Press, Inc., (1972); U.S. Pat. Nos. 4,452,910;5,376,611; and 4,060,480; each of which is incorporated herein in itsentirety.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed above and throughout the text areprovided solely for their disclosure prior to the filing date of thepresent application. Nothing herein is to be construed as an admissionthat the inventors are not entitled to antedate such disclosure byvirtue of prior invention.

For any particular compound disclosed herein, any general structurepresented also encompasses all conformational isomers, regioisomers,stereoisomers, and the like, that can arise from a particular set ofsubstituents. The general structure also encompasses all enantiomers,diastereomers, and other optical isomers whether in enantiomeric orracemic forms, as well as mixtures of stereoisomers, as the contextrequires.

The present invention is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort can be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

In the following examples, unless otherwise specified, the syntheses andpreparations described herein were carried out under an inert atmospheresuch as nitrogen and/or argon. Solvents were purchased from commercialsources and were typically dried over activated alumina prior to use.Unless otherwise specified, reagents were obtained from commercialsources.

General testing procedures, characterization, and synthetic proceduresare provided herein. Synthetic methods to prepare the metallocenes,treated solid oxides, and other reagents of this invention are alsoprovided herein.

General Testing Procedures

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238condition F at 190° C. with a 2,160 gram weight.

High load melt index (HLMI, g/10 min) was determined in accordance withASTM D1238 condition E at 190° C. with a 21,600 gram weight.

Polymer density was determined in grams per cubic centimeter (g/cc) on acompression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D1928, procedure C.

Molecular weight and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, UK) system equipped with a differentialrefractive index detector and three 7.5 mm×300 mm 20 um Mixed A-LScolumns (Polymer Labs) running at 145° C. The flow rate of the mobilephase, 1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT), was set at 1 mL/min and theconcentration of polymer solutions was generally kept in the range of1.0-1.5 mg/mL, depending on the molecular weights. Sample preparationwas conducted at 150° C. for 4 h with occasional and gentle agitationbefore the solutions being transferred to sample vials for injection. Inorder to minimize unbalanced solvent peak, solvent with the samecomposition as the mobile phase was used for solution preparation. Theintegral calibration method was employed to deduce molecular weights andmolecular weight distributions using a Chevron Phillips ChemicalsCompany's broad linear polyethylene, Marlex BHB5003, as the broadstandard. The integral table of the broad standard was pre-determined ina separate experiment with SEC-MALS.

Preparation of a Sulfated Alumina Activator-Support

Sulfated alumina was formed by a process wherein alumina waschemically-treated with a sulfate or bisulfate source, typicallyselected from, but not limited to, sulfuric acid, ammonium sulfate, orammonium bisulfate. One example follows.

A commercial alumina sold as W. R. Grace Alumina A was sulfated byimpregnation with an aqueous solution containing about 15-20% (NH₄)₂SO₄or H₂SO₄. This sulfated alumina was calcined at 550° C. in air (240°C./h ramp rate), with a 3 h hold period at this temperature. Afterward,the alumina was collected and stored under dry nitrogen, and was usedwithout exposure to the atmosphere.

Metallocene Preparations

All manipulations involving air-sensitive reagents and materials wereperformed under nitrogen by using standard Schlenk line or dry boxtechniques. Unless specified otherwise, reagents were typically obtainedfrom Aldrich Chemical Company and were used as received.2,7-Di-tert-butylfluorene was purchased from commercial sourcesincluding Degussa and Aldrich Chemical Company the Grignard reagentCpMgCl (1M in THF) was purchased from Boulder Scientific Company, andhafnium(IV) chloride was purchased from Strem. The solvent THF wasdistilled from potassium, while anhydrous diethyl ether, methylenechloride, pentane, and toluene (Fisher Scientific Company) were storedover activated alumina. All solvents were degassed and stored undernitrogen. Zirconium(IV) chloride (99.5%) and n-butyllithium werepurchased from Aldrich Chemical Company and were used as received.Bis(η⁵-indenyl) zirconium dichloride (M-B) andbis[η⁵-n-butylcyclopentadienyl]zirconium dichloride (M-D) were purchasedfrom commercial sources such as, for example, Strem Chemicals, BoulderScientific and Crompton. Reaction products were analyzed by ¹H NMRspectroscopy (300 MHz, CDCl₃ referenced against either the residualproton peak at 7.24 ppm for CHCl₃ or TMS at 0 ppm) or ¹³C NMR (75 MHz,CDCl₃, referenced against central line of CDCl₃ at 77.00 ppm).

The following fulvenes, F-1 through F-3, were prepared as disclosedherein and used to prepare the ligands L-1 through L-3 as providedherein.

The following ligands L-1 through L-3 were prepared as disclosed herein.

Synthesis of 2-(pent-4-enyl)-6,6-diphenylpentafulvene (F-1)

To 5-bromo-1-pentene (100 g of 95 wt %, 0.637 mol) was addedcyclopentadienyl magnesium chloride (700 mL of 1 M solution in THF, 0.7mol) at 0° C. in an hour. After stirring for an additional 30 minutes at0° C., the mixture was warmed to room temperature. After stirringovernight, the reaction was quenched with a mixture of ice and water.The mixture was extracted with pentane. The organic layer was washedwith water and dried over anhydrous sodium sulfate. Removal of thesolvent under vacuum at room temperature gave a yellow-brown liquid (98g, crude pent-4-enylcyclopentadiene). To the crudepent-4-enylcyclopentadiene (89 g) dissolved in THF (500 mL) was addedn-BuLi (60 mL of 10 M in hexanes, 0.6 mol) at −78° C. The mixture waswarmed up to room temperature and stirred overnight. The anion solutionwas added to benzophenone (110 g, 0.604 mol) dissolved in THF (500 mL)at 0° C. in 25 minutes. The mixture was warmed to room temperature andstirred overnight. The reaction was quenched with a mixture of ice and10% HCl aqueous solution. The mixture was extracted with pentane. Theorganic layer was washed with water and dried over anhydrous sodiumsulfate. Removal of the solvent under vacuum at 40° C. gave a dark redviscous oil. The oil was dissolved in heptane and filtered throughsilica gel. The product was collected by washing the silica gel with5-10% CH₂Cl₂ in heptane. Removal of the solvent gave the desired product(145 g, 84% yield based on 5-bromo-1-pentene) as a dark red viscous oil.¹H NMR (300 MHz, CDCl₃) δ 7.41-7.48 (m, 10H), 6.59-6.62 (dd, J=5.1 Hz,1.4 Hz, 1H), 6.40-6.42 (dd, J=5.1 Hz, 1.4 Hz, 1H), 6.12-6.15 (m, 1H),5.86-6.02 (m, 1H), 5.08-5.20 (m, 2H), 2.55-2.60 (t, J=7.2 Hz, 2H),2.22-2.30 (m, 2H), 1.76-1.88 (quin, J=7.2 Hz, 2H); ¹³C NMR (75 MHz,CDCl₃) δ 148.28, 148.13, 143.28, 140.85, 140.76, 138.01, 133.51, 131.34,131.29, 127.76, 127.74, 127.13, 127.08, 124.74, 118.24, 114.24, 33.95,30.13, 28.46.

Synthesis of1-(3-(pent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(L-1)

To 2,7-di-tert-butylfluorene (125.1 g, 0.45 mol) dissolved in Et₂O (700mL) was added n-BuLi (47 mL of 10 M in hexanes, 0.47 mol) at 0° C. Themixture was warmed to room temperature and stirred overnight. The anionsolution was added to 2-(pent-4-enyl)-6,6-diphenylpentafulvene (F-1)(145 g, 0.487 mol) dissolved in Et₂O (300 mL) at −78° C. in 10 minutes.The mixture was warmed to room temperature and stirred overnight. Thereaction was quenched with a mixture of ice and 10% HCl aqueoussolution. The mixture was extracted with Et₂O. The organic layer waswashed with water and dried over anhydrous sodium sulfate. Removal ofthe solvent under vacuum gave a pale brown solid. The solid was washedwith heptane and dried under vacuum. A mixture of isomers for thedesired product (191.7 g, 74% yield) was obtained as a white solid.

Synthesis of 2-(but-3-enyl)-6,6-diphenylpentafulvene (F-2)

To 4-bromo-1-butene (100 g of 97 wt %, 0.719 mol) was addedcyclopentadienyl magnesium chloride (800 mL of 1 M solution in THF, 0.8mol) at 0° C. in 50 minutes. After stirring for an additional 15 minutesat 0° C., the mixture was warmed to room temperature. After stirringovernight, the reaction was quenched with a mixture of ice and water.The mixture was extracted with pentane. The organic layer was washedwith water and dried over anhydrous sodium sulfate. Removal of thesolvent under vacuum at room temperature gave a brown liquid (94.2 g,crude but-3-enylcyclopentadiene). To the crude but-3-enylcyclopentadiene(94.2 g) dissolved in THF (500 mL) was added n-BuLi (70 mL of 10 M inhexanes, 0.7 mol at −78° C. The mixture was warmed up to roomtemperature and stirred overnight. The anion solution was added tobenzophenone (133.8 g, 0.735 mol) dissolved in THF (400 mL) at 0° C. in35 minutes. The mixture was warmed to room temperature and stirredovernight. The reaction was quenched with a mixture of ice and 10% HClaqueous solution. The mixture was extracted with pentane. The organiclayer was washed with water and dried over anhydrous sodium sulfate.Removal of the solvent under vacuum at 40° C. gave a dark red viscousoil. The oil was dissolved in heptane and filtered through silica gel.The product was collected by washing the silica gel with 5-10% CH₂Cl₂ inheptane. Removal of the solvent gave the desired product (152 g, 74.4%yield based on 4-bromo-1-butene) as a dark red viscous oil. ¹H NMR (300MHz, CDCl₃) δ 7.29-7.41 (m, 10H), 6.50-6.53 (dd, J=5.2 Hz, 1.4 Hz, 1H),6.29-6.31 (dd, J=5.2 Hz, 1.4 Hz, 1H), 6.02-6.05 (m, 1H), 5.82-5.98 (m,1H), 4.94-5.16 (m, 2H), 2.53-2.60 (m, 2H), 2.33-2.43 (m, 2H); ¹³C NMR(75 MHz, CDCl₃) δ 148.59, 147.67, 143.18, 140.86, 140.78, 137.85,133.48, 131.38, 131.36, 127.85, 127.82, 127.18, 127.13, 124.75, 118.35,114.29, 33.36, 30.20.

Synthesis of1-(3-(but-3-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(L-2)

To 2,7-di-tert-butylfluorene (91.7 g, 0.33 mol) dissolved in Et₂O (500mL) was added n-BuLi (35 mL of 10 M in hexanes, 0.35 mol) at 0° C. Themixture was warmed to room temperature and stirred overnight. The anionsolution was added to 2-(but-3-enyl)-6,6-diphenylpentafulvene (compoundF-2) (104 g, 0.366 mol) dissolved in Et₂O (200 mL) at 0° C. in 35minutes. After stirring for an additional 30 minutes at 0° C., themixture was warmed to room temperature and stirred overnight. Thereaction was quenched with a mixture of ice and 10% HCl aqueoussolution. The mixture was extracted with CH₂Cl₂. The organic layer waswashed with water and dried over anhydrous sodium sulfate. Removal ofthe solvent under vacuum gave a pale brown solid. The solid was washedwith heptane and dried under vacuum. A mixture of isomers for thedesired product (142 g, 76.5% yield) was obtained as a white solid.

Synthesis of 2-(1,1-dimethylpent-4-enyl)-6,6-diphenylpentafulvene (F-3)

To a solution of 6-butenyl-6-methylpentafulvene (17.8 g, 122 mmol)(prepared by the method of K. J. Stone and R. D. Little, J. Org. Chem.,1984, 49(11), 1849-1853) in dry THF (50 mL) was added a solution ofmethyllithium (75 mL of 1.6 M in ether, 120 mmol) while cooling in dryice. After stirring for 20 hours and warming to room temperature, theyellow solution was gradually added to a solution of benzophenone (21.87g, 120 mmol) in THF (50 mL) while cooling in ice. A red color formedimmediately and after 4 hours analysis of an aliquot showed that thereaction was nearly complete. After an additional hour, the mixture wascooled while a solution of concentrated hydrochloric acid (20 mL) inwater (200 mL) was added. Following addition of pentane (150 mL), theorganic layer was washed with water and dried over sodium sulfate. Thesolvent was removed under vacuum and the red liquid was cooled to −15°C. overnight. The red crystalline product was washed with cold methanoland dried under vacuum to a red solid (32.8 g, 84% yield). ¹H NMR (300MHz, CDCl₃) δ 7.22-7.40 (m, 10H), 6.56-6.58 (dd, J=5.1 Hz, 1.8 Hz, 1H),6.24-6.26 (dd, J=5.1 Hz, 1.8 Hz, 1H), 5.91-5.93 (t, J=1.8 Hz, 1H),5.70-5.85 (m, 1H), 4.84-5.00 (m, 2H), 1.88-2.00 (m, 2H), 1.52-1.60 (m,2H), 1.17 (s, 6H); ¹³C NMR (75 MHz, CDCl₃) δ 156.16, 148.39, 143.20,140.96, 140.92, 138.98, 131.61, 131.43, 131.39, 127.81, 127.77, 127.24,127.14, 124.88, 116.30, 113.45, 41.96, 35.86, 29.90, 27.90.

Synthesis of1-(3-(1,1-dimethylpent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(L-3)

A solution of 2,7-di-tert-butylfluorene (27.8 g, 100 mmol) in Et₂O (200mL) was cooled in dry ice and n-BuLi (68 mL of 1.6 M in hexanes, 0109mmol) was added dropwise. The slurry was warmed to room temperature andstirred for 24 hours. The dark solution was cooled in dry ice and asolution of 2-(1,1-dimethylpent-4-enyl)-6,6-diphenylpentafulvene(compound F-3) (32.8 g, 54.3 mmol) in Et₂O (100 mL) was then addedrapidly. The mixture was warmed to room temperature and stirred for 20hours. After cooling in ice, a solution of concentrated hydrochloricacid (20 mL) in water (200 mL) was added. Following addition of pentane(100 mL), the organic layer was separated and washed with water. Afterdrying over sodium sulfate and filtering, the solvent was removed undervacuum leaving a glassy solid. The solid was heated with methanol (100mL) and the hot methanol solution was poured off. This process wasrepeated four times. The solid was then dissolved in hot pentane, whichwas then removed under vacuum while heating. The solid was broken up,dried under vacuum, and then heated with ethanol (70 mL). After cooling,the solid was filtered and dried. A mixture of isomers for the desiredproduct (18.1 g, 30% yield) was obtained as a white solid.

Synthesis ofdiphenylmethylidene{η⁵-[3-(pent-4-enyl)cyclopentadien-1-ylidene]}[η⁵-(2,7-di-tert-butylfluoren-9-ylidene)]hafniumdichloride (M-1)

To1-(3-(pent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(compound L-1) (45.3 g, 78.6 mmol) dissolved in Et₂O (400 mL) was slowlyadded n-BuLi (68.5 mL of 2.5 M in hexanes, 171.3 mmol) at 0° C. Themixture was warmed to room temperature, stirred overnight, and thenadded via cannula to HfCl₄ (26.8 g, 83.6 mmol) suspended in a mixture ofpentane (450 mL) and Et₂O (30 mL) at 0° C. in 30 minutes. The mixturewas warmed to room temperature and stirred for two days. The slurry wasconcentrated and centrifuged. The liquid was decanted off. The remainingsolid was washed a second time with pentane (100 mL), then extractedwith methylene chloride and centrifuged. The solution was taken todryness under vacuum to give a yellow solid (46.4 g, 71.7%). ¹H NMR (300MHz, CDCl₃) δ 7.88-7.98 (m, 3H), 7.78-7.88 (m, 3H), 7.40-7.50 (m, 2H),7.29-7.38 (broad t, J=7.2 Hz, 2H), 7.11-7.28 (m, 4H), 6.28 (broad s,1H), 6.24 (broad s, 1H), 5.87-5.93 (t, J=2.7 Hz, 1H), 5.61-5.78 (m, 1H),5.44-5.50 (t, J=2.7 Hz, 1H), 5.19-5.25 (t, J=2.7 Hz, 1H), 4.82-4.96 (m,2H), 2.28-2.48 (m, 2H), 1.94-2.05 (m, 2H), 1.46-1.60 (m, 2H), 0.98 (s,18H); ¹³C NMR (75 MHz, CDCl₃) δ 149.41, 149.21, 144.47, 144.24, 137.71,132.69, 129.08, 128.83, 128.45, 128.39, 128.22, 126.50, 126.46, 126.13,125.97, 123.70, 123.46, 123.40, 123.34, 119.89, 119.66, 119.01, 118.86,118.82, 118.53, 114.75, 114.39, 111.11, 100.92, 100.69, 76.88, 57.88,35.29, 35.27, 33.75, 31.04, 31.02, 29.48, 29.31.

Synthesis ofdiphenylmethylidene{η⁵-[3-(but-3-enyl)cyclopentadien-1-ylidene]}[η⁵-(2,7-di-tert-butylfluoren-9-ylidene)]hafniumdichloride (M-2)

To1-(3-(but-3-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(compound L-2) (3.2 g, 5.7 mmol) dissolved in Et₂O (30 mL) was slowlyadded n-BuLi (5.2 mL of 2.5 M in hexanes, 13 mmol) at 0° C. The mixturewas warmed to room temperature, stirred overnight, and then added viacannula to HfCl₄ (2.1 g, 6.5 mmol) suspended in a mixture of pentane (30mL) and Et₂O (5 mL) at 0° C. in 10 minutes. The mixture was warmed toroom temperature and stirred for two days. The slurry was concentratedand centrifuged. The liquid was decanted off. The remaining solid waswashed a second time with pentane (80 mL), then extracted with methylenechloride and centrifuged. The solution was taken to dryness under vacuumto give a yellow solid (3.1 g, 67.4% yield). ¹H NMR (300 MHz, CDCl₃) δ7.87-7.98 (m, 3H), 7.79-7.86 (m, 3H), 7.43-7.49 (m, 2H), 7.30-7.38 (dt,J=7.5 Hz, 1.4 Hz, 2H), 7.14-7.29 (m, 4H), 6.24-6.27 (d, J=0.6 Hz, 1H),6.20-6.24 (d, J=0.6 Hz, 1H), 5.87-5.92 (t, J=2.7 Hz, 1H), 5.62-5.77 (m,1H), 5.42-5.47 (t, J=2.7 Hz, 1H), 5.18-5.23 (t, J=2.7 Hz, 1H), 4.85-4.98(m, 2H), 2.35-2.55 (m, 2H), 2.13-2.22 (m, 2H), 0.96 (s, 18H); ¹³C NMR(75 MHz, CDCl₃) δ 149.52, 149.33, 144.51, 144.30, 137.33, 132.16,129.13, 128.89, 128.51, 128.45, 128.30, 128.26, 126.58, 126.53, 126.24,126.06, 123.77, 123.54, 123.42, 123.36, 119.97, 119.75, 119.08, 118.90,118.58, 114.94, 114.83, 111.14, 101.01, 100.68, 76.93, 57.94, 35.36,35.35, 34.11, 31.08, 31.05, 29.42.

Synthesis ofdiphenylmethylidene{η⁵-[3-(pent-4-enyl)cyclopentadien-1-ylidene]}[η⁵-(2,7-di-tert-butylfluoren-9-ylidene)]zirconiumdichloride (M-3)

To1-(3-(pent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(compound L-1) (34.7 g, 60.2 mmol) dissolved in Et₂O (300 mL) was slowlyadded n-BuLi (52 mL of 2.5 M in hexanes, 130 mmol) at 0° C. The mixturewas warmed to room temperature, stirred overnight, and then added viacannula to ZrCl₄ (14.7 g, 63.1 mmol) suspended in a mixture of pentane(250 mL) and Et₂O (20 mL) at 0° C. in 30 minutes. The mixture was warmedto room temperature, stirred for one day, and evacuated to dryness. Theresidue was stirred in pentane (200 mL) and centrifuged. The supernatantwas discarded. The remaining solid was washed a second time with pentane(50 mL), then extracted with methylene chloride and centrifuged. Thesolution was taken to dryness under vacuum to give a red solid (33.5 g,75.6%). ¹H NMR (300 MHz, CDCl₃) δ 7.94-7.99 (m, 2H)], 7.89-7.94 (m, 1H),7.77-7.87 (m, 3H), 7.47-7.53 (m, 2H), 7.32-7.39 (dt, J=7.2 Hz, 1.2 Hz,2H), 7.15-7.29 (m, 4H), 6.23 (broad s, 1H), 6.19 (broad s, 1H),5.94-5.98 (t, J=2.7 Hz, 1H), 5.62-5.76 (m, 1H), 5.50-5.54 (t, J=2.7 Hz,1H), 5.24-5.29 (t, J=2.7 Hz, 1H), 4.82-4.96 (m, 2H), 2.23-2.43 (m, 2H),1.97-2.05 (m, 2H), 1.48-1.61 (m, 2H), 0.97 (s, 18H); ¹³C NMR (75 MHz,CDCl₃) δ 149.85, 149.65, 144.27, 144.03, 137.79, 134.18, 129.11, 128.85,128.51, 128.46, 128.34, 126.59, 126.55, 126.18, 126.03, 124.04, 123.79,123.54, 123.47, 121.09, 120.89, 120.32, 120.06, 119.46, 119.26, 115.61,114.44, 108.51, 103.36, 103.29, 76.69, 58.13, 35.39, 35.37, 33.78,31.06, 31.03, 29.61, 29.33.

Synthesis ofdiphenylmethylidene{η⁵-[3-(but-3-enyl)cyclopentadien-1-ylidene]}[η⁵-(2,7-di-tert-butylfluoren-9-ylidene)]zirconiumdichloride (M-4)

To1-(3-(but-3-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(compound L-2) (40.5 g, 72.1 mmol) suspended in Et₂O (400 mL) was slowlyadded n-BuLi (15.2 mL of 10 M in hexanes, 152 mmol) at 0° C. The mixturewas warmed to room temperature, stirred overnight, and then added viacannula to ZrCl₄ (18.5 g, 79.4 mmol) suspended in a mixture of pentane(400 mL) and Et₂O (30 mL) at 0° C. in 15 minutes. The mixture was warmedto room temperature, stirred for one day, and evacuated to dryness. Theresidue was stirred in pentane (300 mL) and centrifuged. The supernatantwas discarded. The remaining solid was washed a second time with pentane(100 mL), then extracted with methylene chloride and centrifuged. Thesolution was taken to dryness under vacuum to give a red solid (38.1 g,73.3% yield). ¹H NMR (300 MHz, CDCl₃) δ 7.88-8.02 (m, 3H), 7.77-7.88 (m,3H), 7.46-7.54 (m, 2H), 7.31-7.40 (broad t, J=7.5 Hz, 2H), 7.14-7.32 (m,4H), 6.24 (s, 1H), 6.20 (s, 1H), 5.96-6.02 (unresolved t, 1H), 5.63-5.79(m, 1H), 5.50-5.55 (unresolved t, 1H), 5.25-5.31 (unresolved t, 1H),4.87-5.01 (m, 2H), 2.33-2.53 (m, 2H), 2.15-2.27 (m, 2H), 0.97 (s, 18H);¹³C NMR (75 MHz, CDCl₃) δ 149.85, 149.65, 144.23, 144.01, 137.27,133.51, 129.08, 128.84, 128.50, 128.45, 128.33, 128.30, 126.58, 126.54,126.18, 126.01, 124.04, 123.81, 123.55, 123.48, 121.08, 120.89, 120.31,120.03, 119.43, 119.24, 115.71, 114.86, 108.44, 103.37, 103.18, 76.66,58.10, 35.38, 35.36, 33.98, 31.05, 31.02, 29.46.

Synthesis ofdiphenylmethylidene{η⁵-[3-(1,1-dimethylpent-4-enyl)cyclo-pentadien-1-ylidene]}[η⁵-(2,7-di-tert-butylfluoren-9-ylidene)]zirconiumdichloride (M-5)

A slurry of1-(3-(1,1-dimethylpent-4-enyl)cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane(compound L-3) (10.8 g, 17.9 mmol) in Et₂O (50 mL) was cooled in dry iceand n-BuLi (22.2 mL of 1.6 M in hexanes, 35.5 mmol) was added dropwise.After 1 hour, the bath was removed and the mixture was stirred for 48hours at room temperature. The mixture was added to ZrCl₄ (4.37 g, 18.8mmol) suspended in pentane (50 mL) while cooling in ice. The slurry wasstirred for 65 hours at room temperature. The slurry was concentrateduntil thick and pentane (70 mL) was added. The slurry was stirredovernight and the liquid was decanted off. The solid was washed a secondtime with pentane and then extracted with methylene chloride andcentrifuged. The solution was taken to dryness under vacuum to give ared solid (11.65 g, 85.2% yield). ¹H NMR (300 MHz, CDCl₃) δ 7.93-8.02(m, 3H), 7.80-7.91 (m, 3H), 7.52-7.60 (dt, J=8.7 Hz, 1.5 Hz, 2H),7.38-7.47 (m, 2H), 7.20-7.35 (m, 4H), 6.27 (broad s, 2H), 6.14-6.18 (t,J=3.0 Hz, 1H), 5.67-5.83 (m, 1H), 5.61-5.64 (t, J=3.0 Hz, 1H), 5.48-5.52(t, J=3.0 Hz, 1H), 4.88-5.04 (m, 2H), 1.76-2.10 (m, 2H), 1.44-1.53 (m,2H), 1.26 (s, 3H), 1.07 (s, 3H), 1.02 (s, 18H); ¹³C NMR (75 MHz, CDCl₃)δ 149.67, 149.60, 144.31, 144.13, 143.46, 138.49, 129.15, 128.89,128.51, 128.48, 128.39, 128.33, 126.58, 126.52, 126.11, 125.97, 124.18,124.10, 123.73, 123.36, 121.09, 120.78, 120.20, 119.75, 118.88, 114.16,113.84, 108.10, 104.30, 100.60, 77.19, 57.65, 46.43, 36.32, 35.38,35.36, 31.06, 31.03, 29.47, 26.99, 24.19.

Synthesis of bis[(η⁵-1-(3-phenylpropyl)indenyl)]zirconium dichloride(M-A)

This metallocene was prepared according to the general preparativemethod for substituted bis(indenyl) metallocenes reported in: Alt, H G.,et. al. J. Organomet. Chem. 2000, 599, 275; and Alt, H G., et. al. J.Organomet. Chem. 2001, 621, 304. General preparative methods for formingsubstituted bis(indenyl)metallocenes are reported in a number ofreferences.

Synthesis of bis(η⁵-indenyl)zirconium dibenzyl (M-C)

This metallocene was prepared according to the general preparativemethod for forming hydrocarbyl-substituted metallocenes by substitutionreactions, such as alkylating metallocene chlorides, as reported in:Resconi, L., et. al. J. Organomet. Chem. 2003, 683, 2; Basset, J.-M.,et. al. J. Am. Chem. Soc., 2001, 123, 3520; Marks, T. J. Acc. Chem.Res., 1992, 25, 57; and Marks, T. J. Organometallics, 2602, 21, 1788.General preparative methods for forming hydrocarbyl-substitutedmetallocenes are reported in a number of references.

Synthesis of{η⁵-[1-(prop-2-enyl)indenyl]}[η⁵-(n-butylcyclopentadienyl)]-zirconiumdichloride (M-E)

A 500 mL Schlenk flask was charged with (n-BuC₅H₄)ZrCl₃ (20.0 g, 62.7mmol; prepared by the reaction of (n-BuC₅H₄)₂ZrCl₂ and ZrCl₄ inrefluxing toluene) and approximately 400 mL of diethyl ether. Theresulting slurry was cooled to 0° C., after which time Li(1-allylindene)(10.7 g, 66.0 mmol) was added via cannula as an ethereal solution. Thereaction mixture was stirred overnight at ambient temperature and thesolvent was removed in vacuo. The resulting solid was dissolved intoluene and centrifuged to remove LiCl. Removal of solvent in vacuoyielded a yellow-brown solid which was dissolved in adichloromethane/pentane mixture and was cooled to −35° C. for a coupleof hours. Resulting slurry was filtered, and the precipitate was driedunder reduced pressure (0.1 mm, 1 h) to yield the product as a yellowsolid (17.0 g, 62%). ¹H NMR (CDCl₃, δ) 0.87 (t, J=7.2 Hz, CH₃),1.50-1.22 (m, CH₂(CH₂)₂CH₃), 2.58-2.42 (m, CH₂(CH₂)₂CH₃), 3.77-3.62 (m,CH₂═CHCH₂), 5.10-5.02 (m, CH₂═CHCH₂), 5.78-5.76 (m, 1, C₅H₄), 5.87-5.83(m, 2, C₅H₄), 5.99-5.91 (m, CH₂═CHCH₂), 6.04-6.00 (m, 1, C₅H₄),6.39-6.37 (m, 1, C₉H₆), 6.63 (d, J=3.0 Hz, 1, C₉H₆), 7.28-7.18 (m, 2,C₉H₆), 7.60-7.56 (m, 2, C₉H₆).

Examples 1-6 Bench Scale Catalytic Runs Varying the Metallocene,Activator-Support, and Conditions

Examples 1-6 in Table 1 illustrate polymerization run data and polymercharacterization data for ethylene homopolymer and ethylene-1-hexenecopolymer prepared using the catalyst compositions disclosed herein.Polymerization runs were conducted in a one-gallon (3.785 liter)stainless steel reactor. Two liters of isobutane and alkyl aluminumcocatalyst/scavenger were used in all examples. Hydrogen, when added,was added slowly throughout the run and was measured as the pressuredrop on a 340 mL steel cylinder. Metallocene solutions (1 mg/mL) wereusually prepared by dissolving 30 mg of metallocene in 30 mL of toluene.

A typical polymerization procedure is as follows: Alkyl aluminum, SSAand the metallocene solution were added in that order through a chargeport while venting isobutane vapor. The charge port was closed and twoliters of isobutane were added. The contents of the reactor were stirredand heated to the desired run temperature. Hexene, when added, wasflushed into the reactor as the ethylene was initially added. Ethylenewas fed on demand to maintain the specified pressure for the specifiedlength of the polymerization run. The reactor was maintained at thedesired run temperature through the run by an automated heating-coolingsystem

FIG. 2 provides comparison gel permeation chromatograms (GPCs) forethylene homopolymers and copolymers of Examples 1-6 (E1-E6), preparedas provided in Table 1. Formulas for the particular metallocenes used inExamples 1-6 are illustrated in FIG. 1.

Examples 7-13 Pilot-Plant Scale Catalytic Runs Varying the Metallocene,Activator-Support, and Conditions

Examples 7-13 (E7-E13) in Table 2 illustrate polymerization run data andpolymer characterization data for ethylene-1-hexene copolymer preparedusing the catalyst compositions disclosed herein. Polymerization runswere conducted as follows. A 27.3-gallon slurry loop reactor wasemployed as the polymerization reactor. Polymerization runs were carriedout under continuous particle form process conditions in the loopreactor (also known as a slurry process) by contacting an isobutanesolution of a first metallocene, having the formula indicated in FIG. 1,and a second metallocene, having the formula indicated in FIG. 1, witheither triisobutylaluminum or tributylaluminum and a sulfated aluminaactivator-support in a 0.5 L stirred autoclave with continuous output tothe loop reactor.

Precontacting was carried out in the following manner. Eithertriisobutylaluminum or tributylaluminum solution and both metallocenesolutions in isobutane were fed as separate streams into a manifoldupstream of the solid activator feeder outlet where they contacted eachother and were combined with isobutane flush. The solid activator wasflushed with the combined solution into the autoclave, brieflycontacting the either triisobutylaluminum ortributylaluminum/metallocenes mixture/solid activator just beforeentering the autoclave. The combined solution flush used to transportthe solid activator into the autoclave was set at a rate that wouldresult in a residence time of approximately 6-24 minutes in theautoclave by adjusting the isobutane flow rate. The total flow from theautoclave then entered the loop reactor.

Ethylene used was polymerization grade ethylene (obtained from UnionCarbide Corporation) which was purified through a column of aluminaactivated at 250° C. (482° F.) in nitrogen. 1-Hexene used waspolymerization grade 1-hexene (obtained from Chevron Chemicals Company)which was further purified by distillation and subsequently passedthrough a column of alumina activated at 250° C. (482° F.) in nitrogen.The loop reactor was a liquid full, 15.2 cm diameter, loop reactor,having a volume of 27.3 gallons (103.3 liters). Liquid isobutane wasused as the diluent. Some hydrogen was added to regulate the molecularweight of the low molecular weight component of the polymer product. Theisobutane was polymerization grade isobutane (obtained from PhillipsPetroleum Company, Borger, Tex.) that was further purified bydistillation and subsequently passed through a column of aluminaactivated at 250° C. (482° F.) in nitrogen.

Reactor conditions included a pressure around 580 psi (4 MPa), and atemperature about 77-95° C. (170-203° F.) as indicated in Table 2. Also,the reactor was operated to have a residence time of about 1.1 hours.The solid activator was added through a 0.35 cc circulating ball-checkfeeder and fed to the 0.5-Liter autoclave as described above.Metallocene concentrations in the reactor were within a range of about1.32 to 3.58 parts per million (ppm) of the diluent in thepolymerization reactor. Polymer was removed from the reactor at the rateof about 22-27 lbs per hour and recovered in a flash chamber. A Vulcandryer was used to dry the polymer under nitrogen at about 60-80° C.(140-176° F.).

The cocatalyst (TIBA or TNBA) was added in a concentration in a range offrom about 110 to 201 parts per million of the diluent in thepolymerization reactor. To prevent static buildup of the reactor, asmall amount (less than 5 ppm, by weight, of diluent) of a commercialantistatic agent sold as “Stadis 450” was usually added. The variousresins were prepared according to the above procedure, as specified inTable 2.

FIG. 3 provides comparison gel permeation chromatograms (GPCs) forethylene homopolymers and copolymers of Examples 7-13 (E7-E13), preparedas provided in Table 2. Formulas for the particular metallocenes used inExamples 7-13 are illustrated in FIG. 1.

TABLE 1 Laboratory polymerization conditions and polymerization results.H₂ Support- Reactor (340 mL Activator Example First Second Time TempPressure vessel, 1-Hexene Support- weight No. Metallocene ¹ Metallocene¹ (min) (° C.) (psi) Δ psi) (g) Activator (mg) E1   1 mg 2.1 mg 30 95420 30 0.0 Sulfated 200 M-B M-1 Alumina E2   1 mg 1.5 mg 60 95 450 300.0 Sulfated 100 M-B M-1 Alumina E3 1.5 mg 1.5 mg 60 90 450 30 10.0Sulfated 100 M-A M-1 Alumina E4 1.5 mg 1.5 mg 60 90 450 30 0.0 Sulfated100 M-E M-1 Alumina E5   1 mg 2.1 mg 30 95 420 0.0 Sulfated 200 M-B M-1Alumina E6 1.5 mg 1.5 mg 30 95 450 0 0.0 Sulfated 91 M-D M-1 AluminaExample R₃Al² Solid No. (mmol) PE (g) MI HLMI Mn/1000 Mw/1000 Mz/1000 HIE1 0.25 351 0.0 3.40 19.24 540.77 2194.97 28.11 TIBA E2 0.25 472 0.00.62 26.55 748.46 3815.97 28.19 TIBA E3 0.25 270 0.0 1.48 11.28 640.723240.33 56.8 TIBA E4 0.25 421 0.0 1.65 20.68 523.35 2185.03 25.31 TIBAE5 0.25 206 0.0 0.03 98.95 1269.04 3823.54 12.83 TIBA E6 0.5 139 0.00.008 78.21 900.05 3182.16 12.83 TIBA ¹ Metallocene formulas areillustrated in FIG. 1. ² TIBA, triisobutylaluminum.

TABLE 2 Pilot plant polymerization conditions and polymerizationresults. Example No. E7 E8 E9 E10 E11 E12 E13 Activator-Support SulfatedSulfated Sulfated Sulfated Sulfated Sulfated Sulfated Alumina AluminaAlumina Alumina Alumina Alumina Alumina MetalloceneS ¹ M-1 + M-E M-1 +M-E M-1 + M-E M-1 + M-E M-4 + M-C M-4 + M-C M-4 + M-E Metallocene toM-1: 2.51 M-1: 2.25 M-1: 2.37 M-1: 2.51 M-4: 0.27 M-4: 0.27 M-4: 0.49Reactor (ppm) M-E: 1.07 M-E: 1.02 M-E: 1.06 M-E: 1.05 M-C: 0.79 M-C:0.78 M-C: 0.83 Autoclave Residence 15.57 14.68 14.37 14.17 22.91 23.226.13 Time (Min) Cocatalyst Type ² TIBA TIBA TIBA TIBA TNBA TNBA TNBACocatalyst 20.02 + 181.48 19 + 168.5 20.02 + 174.5 19.69 + 89.5 87.82 +44.58 87.26 + 45.14 85.7 + 40.16 (precontactor + reactor) (ppm) Rx Temp(° F.) 202.9 202.9 202.8 202.8 179.7 179.7 169.6 Ethylene (mol %) 15.1513.93 14.42 15.12 13.85 13.64 15.22 1-hexene (mol %) 0.55 0.49 0.45 0.440.79 0.79 0.75 C6═/C2═ (Mole Ratio) 0.04 0.04 0.03 0.03 0.06 0.06 0.05H₂ (mlb/hr) 6 8 8 8 4.6 4.6 8 C2═ Feed Rate (lb/hr) 29.61 29.59 29.5329.60 31.30 31.30 32.1 1-Hexene Feed Rate 0.56 0.61 0.61 0.61 1.21 1.241.01 (lb/hr) Total iC4 Flow Rate 59.3 61.48 60.1 60.07 57.88 57.89 62.67(lb/hr) Solids Conc. wt. % 24.63 24.22 24.23 24.3 28.25 28.61 26.09Polymer Production 22.48 22.67 22.33 22.42 26.00 26.33 25.44 (lb/hr)Density (pellets) (g/cc) 0.9533 0.9517 0.952 0.9529 0.9497 0.9493 0.953Mw/1000 (pellets) 317.04 292.07 276.43 264.06 283.45 281.93 261.8Mn/1000 (pellets) 13.48 8.59 8.31 8.09 13.03 14.44 10.1 Mw/Mn (pellets)23.5 34 33.3 32.6 21.8 19.5 25.9 ¹ Metallocene formulas are illustratedin FIG. 1. ² TIBA, triisobutylaluminum; TNBA, tri-n-butylaluminum.

1. A composition comprising a contact product of: 1) at least one firstmetallocene; 2) at least one second metallocene; and 3) at least oneactivator-support, wherein: a) the at least one first metallocenecomprises an ansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-A),  wherein M¹ is titanium, zirconium, orhafnium; (X¹) and (X²) are independently a substituted cyclopentadienyl,a substituted indenyl, or a substituted fluorenyl; one substituent on(X¹) and (X²) is a bridging group having the formula ER¹R², wherein E isa carbon atom, a silicon atom, a germanium atom, or a tin atom, and E isbonded to both (X¹) and (X²), and wherein R¹ and R² are independently analkyl group or an aryl group, either of which having up to 12 carbonatoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;at least one substituent on (X¹) or (X²) is a substituted or anunsubstituted alkenyl group having up to 12 carbon atoms; (X³) and (X⁴)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl, substituted indenyl, substituted fluorenyl, orsubstituted alkenyl group is independently an aliphatic group, anaromatic group, a cyclic group, a combination of aliphatic and cyclicgroups, an oxygen group, a sulfur group, a nitrogen group, a phosphorusgroup, an arsenic group, a carbon group, a silicon group, or a borongroup, any of which having from 1 to 20 carbon atoms; a halide; orhydrogen; b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-A),  wherein M² is titanium, zirconium, orhafnium; (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,a substituted cyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(B) ₂ or SO₃R^(B), wherein R^(B)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any substituent on the substituted cyclopentadienyl orsubstituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 20 carbon atoms; a halide; or hydrogen;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-A),  wherein M³ is titanium, zirconium,or hafnium; (X⁹) is a substituted cyclopentadienyl group, wherein onesubstituent is an aliphatic group, an aromatic group, or a combinationof aliphatic and cyclic groups, any of which having up to 20 carbonatoms; (X¹⁰) is a substituted indenyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms; (X¹¹) and(X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(C) ₂ or SO₃R^(C), wherein R^(C)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl or substituted indenyl is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, ora boron group, any of which having from 1 to 20 carbon atoms; a halide;or hydrogen; or iii) any combination thereof; and c) the at least oneactivator-support comprises a solid oxide treated with anelectron-withdrawing anion.
 2. A composition according to claim 1,wherein the metallocene (X⁵)(X⁶)(X⁷)(X⁸)M² (M2-A) has the formula:(X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-B), wherein M² is zirconium or hafnium; (X⁵) and(X⁶) are independently a cyclopentadienyl, an indenyl, a substitutedcyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸) areindependently a hydrocarbyl group having up to 12 carbon atoms, H, BH₄,F, Cl, Br, or I; and any substituent on the substituted cyclopentadienylor substituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anyof which having from 1 to 20 carbon atoms.
 3. A composition according toclaim 1, wherein the metallocene (X⁹)(X¹⁰)(X¹¹)(X¹²)M³ (M3-A) has theformula:(X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-B), wherein M³ is zirconium or hafnium; (X⁹)is a substituted cyclopentadienyl group, wherein any substituent isindependently a linear or branched alkyl group having up to 12 carbonatoms; (X¹⁰) is a substituted indenyl group, wherein any substituent isindependently an aliphatic group, an aromatic group, or a combination ofaliphatic and cyclic groups, any of which having from 1 to 20 carbonatoms; and (X¹¹) and (X¹²) are independently a hydrocarbyl group havingup to 12 carbon atoms, H, BH₄, F, Cl, Br, or I.
 4. A compositionaccording to claim 1, wherein the at least one second metallocenecomprises an unbridged metallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-B), wherein M² is zirconium or hafnium; (X⁵)and (X⁶) are independently a cyclopentadienyl, an indenyl, a substitutedcyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸) areindependently a hydrocarbyl group having up to 12 carbon atoms, H, BH₄,F, Cl, Br, or I; and any substituent on the substituted cyclopentadienylor substituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anyof which having up from 1 to 20 carbon atoms;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-B),  wherein M³ is zirconium or hafnium;(X⁹) is a substituted cyclopentadienyl group, wherein any substituent isindependently a linear or branched alkyl group having up from 1 to 12carbon atoms; (X¹⁰) is a substituted indenyl group, wherein anysubstituent is independently an aliphatic group, an aromatic group, or acombination of aliphatic and cyclic groups, any of which having from 1to 20 carbon atoms; and (X¹¹) and (X¹²) are independently a hydrocarbylgroup having up to 12 carbon atoms, H, BH₄, F, Cl, Br, or I; or iii) anycombination thereof.
 5. A composition according to claim 1, wherein theat least one first metallocene comprises a compound having the formula:

wherein M^(1A) is titanium, zirconium, or hafnium; X^(3A) and X^(4A) areindependently F, Cl, Br, I, benzyl, phenyl, or methyl; E^(A) is C or Si;R^(1A) and R^(2A) are independently an alkyl group or an aryl group,either of which having up to 12 carbon atoms, or hydrogen, wherein atleast one of R^(1A) and R^(2A) is an aryl group; R^(3A) and R^(4A) areindependently H or CH₃; n is an integer from 0 to 5 inclusive; andR^(5A) and R^(6A) are independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 12 carbon atoms; or hydrogen.
 6. A compositionaccording to claim 1, wherein the at least one second metallocenecomprises a compound having the formula: i)

 or any combination thereof, wherein M^(2A) is, independently, zirconiumor hafnium; X^(7A) and X^(8A), in each occurrence, are independently F,Cl, Br, I, benzyl, phenyl, or methyl; and R^(7A) and R^(8A), in eachoccurrence, are independently H, methyl, ethyl, n-propyl, n-butyl,n-pentyl, CH₂CH₂CH₂Ph, CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂; ii)

 wherein M^(3A) is zirconium or hafnium; R^(9A) is H or CH₃; R^(10A) isH, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, orCH₂CH₂CH₂CH₃; and X^(11A) and X^(12A) are independently F, Cl, Br, I,benzyl, phenyl, or methyl; or iii) any combination thereof.
 7. Acomposition according to claim 1, wherein the at least oneactivator-support is a solid oxide treated with an electron-withdrawinganion, wherein: the solid oxide is silica, alumina, silica-alumina,aluminophosphate, aluminum phosphate, zinc aluminate,heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or any combination thereof; and theelectron-withdrawing anion is fluoride, chloride, bromide, iodide,phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate,trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstitutedalkanesulfonate, substituted or unsubstituted arenesulfonate, or anycombination thereof.
 8. A composition according to claim 1, wherein thesolid oxide treated with an electron withdrawing anion further comprisesa metal or metal ion selected from zinc, nickel, vanadium, tungsten,molybdenum, silver, tin, or any combination thereof.
 9. A compositionaccording to claim 1, wherein the at least one first metallocenecomprises a compound having the formula:

wherein M^(1B) is zirconium or hafnium; R^(2B) is methyl or phenyl;R^(3B) and R^(4B) are independently H or CH₃; and n is an integer from 0to 5, inclusive.
 10. A composition according to claim 1, wherein the atleast one first metallocene is selected from

or any combination thereof.
 11. A composition according to claim 1,wherein the at least one second metallocene comprises a compound havingthe formula:

or any combination thereof, wherein M^(2B) is zirconium or hafnium;X^(7B) and X^(8B) are independently benzyl, Cl, or methyl; and R^(7B)and R^(8B) are independently H, methyl, ethyl, n-propyl, n-butyl,CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂.
 12. A composition accordingto claim 1, wherein the at least one second metallocene comprises acompound having the formula:

or any combination thereof.
 13. A composition according to claim 1,wherein the at least one second metallocene comprises a compound havingthe formula:

wherein M^(3B) is zirconium or hafnium; R^(9B) is H or CH₃; and R^(10B)is H, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, or CH₂CH₂CH₂CH₃.
 14. Acomposition according to claim 1, wherein the at least one secondmetallocene is selected from

or any combination thereof.
 15. A composition according to claim 1,wherein: a) the at least one first metallocene comprises a compoundhaving the formula:

 wherein M^(1B) is zirconium or hafnium; R^(2B) is methyl or phenyl;R^(3B) and R^(4B) are independently H or CH₃; and n is an integer from 0to 5, inclusive; b) the at least one second metallocene comprises acompound having the formula: i)

 wherein M^(2C) is zirconium or hafnium; and X^(7C) and X^(8C) areindependently benzyl, Cl, or methyl; ii)

 wherein M^(3B) is zirconium or hafnium; R^(9B) is H or CH₃; and R^(10B)is H, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, or CH₂CH₂CH₂CH₃; or iii) anycombination thereof.
 16. A composition according to claim 1, wherein amolar ratio of the at least one first metallocene to the at least onesecond metallocene in the composition is from about 1:10 to about 10:1.17. A composition according to claim 1, wherein the at least oneactivator-support is selected from chlorided alumina, fluorided alumina,fluorided aluminophosphate, sulfated alumina, fluorided silica-alumina,or any combination thereof.
 18. A composition according to claim 1,wherein the contact product further comprises: 4) at least oneorganoaluminum compound having the formula:Al(X¹³)_(n)(X¹⁴)_(3-n), wherein (X¹³) is a hydrocarbyl having from 1 to20 carbon atoms; (X¹⁴) is an alkoxide or an aryloxide, any of whichhaving from 1 to 20 carbon atoms, halide, or hydride; and n is a numberfrom 1 to 3, inclusive.
 19. A composition according to claim 18, whereinthe at least one organoaluminum compound comprises trimethylaluminum,triethylaluminum, tripropylaluminum, tributylaluminum,triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminumethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or anycombination thereof.
 20. A composition according to claim 18, wherein:a) the at least one first metallocene comprises a compound having theformula:

 wherein M^(1A) is zirconium or hafnium; X^(3A) and X^(4A) areindependently F, Cl, Br, I, benzyl, phenyl, or methyl; E^(A) is C or Si;R^(1A) and R^(2A) are independently an alkyl group or an aryl group,either of which having up to 12 carbon atoms, or hydrogen, wherein atleast one of R^(1A) and R^(2A) is an aryl group; R^(3A) and R^(4A) areindependently H or CH₃; n is an integer from 0 to 5, inclusive; andR^(5A) and R^(6A) are independently a hydrocarbyl group an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, ora boron group, any of which having from 1 to 12 carbon atoms; orhydrogen; b) the at least one second metallocene comprises a compoundhaving the formula: i)

 or any combination thereof, wherein M^(2A) is, independently, zirconiumor hafnium; X^(7A) and X^(8A), in each occurrence, are independently F,Cl, Br, I, benzyl, phenyl, or methyl; and R^(7A) and R^(8A), in eachoccurrence, are independently H, methyl, ethyl, n-propyl, n-butyl,n-pentyl, CH₂CH₂CH₂Ph, CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂; ii)

 wherein M^(3A) is zirconium or hafnium; R^(9A) is H or CH₃; R^(10A) isH, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, orCH₂CH₂CH₂CH₃; and X^(11A) and X^(12A) are independently F, Cl, Br, I,benzyl, phenyl, or methyl; or iii) any combination thereof; c) the atleast one organoaluminum compound comprises trimethylaluminum,triethylaluminum, tripropylaluminum, tributyl aluminum,triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminumethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or anycombination thereof; and d) the at least one activator-support comprisesa solid oxide treated with an electron-withdrawing anion, wherein: thesolid oxide is silica, alumina, silica-alumina, aluminophosphate,aluminum phosphate, zinc aluminate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or anycombination thereof; and the electron-withdrawing anion is fluoride,chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate,fluoroborate, fluoro sulfate, trifluoroacetate, phosphate,fluorophosphate, fluorozirconate, fluoro silicate, fluorotitanate,permanganate, substituted or unsubstituted alkanesulfonate, substitutedor unsubstituted arenesulfonate, or any combination thereof.
 21. Acomposition according to claim 18, wherein: a) the at least one firstmetallocene comprises

or any combination thereof; b) the at least one second metallocenecomprises

or any combination thereof; c) the at least one organoaluminum compoundcomprises triethylaluminum, tn-n-butylaluminum, triisobutylaluminum, orany combination thereof; and d) the at least one activator-supportcomprises a sulfated solid oxide.
 22. A composition according to claim18, wherein: a) the at least one first metallocene is selected from

or any combination thereof; b) the at least one second metallocene isselected from

or any combination thereof; c) the at least one organoaluminum compoundcomprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, orany combination thereof; and d) the at least one activator-supportcomprises a sulfated alumina.
 23. A composition according to claim 1,wherein the contact product further comprises: 5) an ionizing ioniccompound selected from tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)-ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate,lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate,lithium tetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl) borate,sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethyl-phenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate,triphenylcarbenium tetrakis(p-tolyl)aluminate, triphenylcarbeniumtetrakis(m-tolyl)aluminate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate, tropyliumtetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate,tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropyliumtetrakis(3,5-dimethylphenyl)aluminate, tropyliumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate,potassium tetrakis(m-tolyl)-aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,triphenylcarbenium tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate,silver tetrakis(1,1,1,3,3,3-hexafluoroisopropanolato)-aluminate, orsilver tetrakis(perfluoro-t-butoxy)aluminate, or any combinationthereof.
 24. A catalyst composition comprising a contact product of: 1)at least one first metallocene; 2) at least one second metallocene; 3)optionally, at least one organoaluminum compound; and 4) at least oneactivator-support, wherein: a) the at least one first metallocenecomprises an ansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-A),  wherein M¹ is titanium, zirconium, orhafnium; (X¹) and (X²) are independently a substituted cyclopentadienyl,a substituted indenyl, or a substituted fluorenyl; one substituent on(X¹) and (X²) is a bridging group having the formula ER¹R², wherein E isa carbon atom, a silicon atom, a germanium atom, or a tin atom, and E isbonded to both (X¹) and (X²), and wherein R¹ and R² are independently analkyl group or an aryl group, either of which having up to 12 carbonatoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;at least one substituent on (X¹) or (X²) is a substituted or anunsubstituted alkenyl group having up to 12 carbon atoms; (X³) and (X⁴)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl, substituted indenyl, substituted fluorenyl, orsubstituted alkenyl group is independently an aliphatic group, anaromatic group, a cyclic group, a combination of aliphatic and cyclicgroups, an oxygen group, a sulfur group, a nitrogen group, a phosphorusgroup, an arsenic group, a carbon group, a silicon group, or a borongroup, any of which having from 1 to 20 carbon atoms; a halide; orhydrogen; b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-A),  wherein M² is titanium, zirconium, orhafnium; (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,a substituted cyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(B) ₂ or SO₃R^(B), wherein R^(B)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any substituent on the substituted cyclopentadienyl orsubstituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 20 carbon atoms; a halide; or hydrogen;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-A),  wherein M³ is titanium, zirconium,or hafnium; (X⁹) is a substituted cyclopentadienyl group, wherein onesubstituent is an aliphatic group, an aromatic group, or a combinationof aliphatic and cyclic groups, any of which having up to 20 carbonatoms; (X¹⁰) is a substituted indenyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms; (X¹¹) and(X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(C) ₂ or SO₃R^(C), wherein R^(C)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl or substituted indenyl is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, ora boron group, any of which having from 1 to 20 carbon atoms; a halide;or hydrogen; or iii) any combination thereof; c) the at least one organoaluminum compound comprises a compound having the formula:Al(X¹³)_(n)(X¹⁴)_(3-n), wherein (X¹³) is a hydrocarbyl having from 1 to20 carbon atoms; (X¹⁴) is an alkoxide or an aryloxide, any of whichhaving from 1 to 20 carbon atoms, halide, or hydride; and n is a numberfrom 1 to 3, inclusive; and d) the at least one activator-supportcomprises a solid oxide treated with an electron-withdrawing anion;wherein the at least one organoaluminum compound is optional when atleast one of the following conditions exist: 1) a) at least one of (X³)and (X⁴) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;b) at least one of (X⁷) and (X⁸) is a hydrocarbyl group having up to 20carbon atoms, H, or BH₄; and c) at least one of (X¹¹) and (X¹²) is ahydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 2) thecatalyst composition comprises at least one organoaluminoxane compound;or 3) both conditions 1 and 2 exist.
 25. A catalyst compositioncomprising a contact product of: 1) at least one first metallocene; 2)at least one second metallocene; and 3) at least one activator-support,wherein: a) the at least one first metallocene comprises anansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-B),  wherein M¹ is titanium, zirconium, orhafnium; (X¹) and (X²) are independently a substituted cyclopentadienyl,a substituted indenyl, or a substituted fluorenyl; one substituent on(X¹) and (X²) is a bridging group having the formula ER¹R², wherein E isa carbon atom, a silicon atom, a germanium atom, or a tin atom, and E isbonded to both (X¹) and (X²), and wherein R¹ and R² are independently analkyl group or an aryl group, either of which having up to 12 carbonatoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;at least one substituent on (X¹) or (X²) is a substituted or anunsubstituted alkenyl group having up to 12 carbon atoms; (X³) and (X⁴)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; wherein at least one of (X³) and (X⁴) is a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; and any additional substituenton the substituted cyclopentadienyl, substituted indenyl, substitutedfluorenyl, or substituted alkenyl group is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, ora boron group, any of which having from 1 to 20 carbon atoms; a halide;or hydrogen; b) the at least one second metallocene comprises anunbridged metallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-C),  wherein M² is titanium, zirconium, orhafnium; (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,a substituted cyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(B) ₂ or SO₃R^(B), wherein R^(B)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; wherein at least one of (X⁷) and (X⁸) is a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; and any substituent on thesubstituted cyclopentadienyl or substituted indenyl is independently analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, or a boron group, any of which having from 1 to 20 carbon atoms;a halide; or hydrogen;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-C),  wherein M³ is titanium, zirconium,or hafnium; (X⁹) is a substituted cyclopentadienyl group, wherein onesubstituent is an aliphatic group, an aromatic group, or a combinationof aliphatic and cyclic groups, any of which having up to 20 carbonatoms; (X¹⁰) is a substituted indenyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms; (X¹¹) and(X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(C) ₂ or SO₃R^(C), wherein R^(C)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; wherein at least one of (X¹¹) and (X¹²) is a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; and any additional substituenton the substituted cyclopentadienyl or substituted indenyl isindependently an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, or a boron group, any of which having from 1 to20 carbon atoms; a halide; or hydrogen; or iii) any combination thereof;and c) the at least one activator-support comprises a solid oxidetreated with an electron-withdrawing anion.
 26. A catalyst compositionaccording to claim 25, wherein the metallocene (X⁵)(X⁶)(X⁷)(X⁸)M² (M2-C)has the formula:(X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-D), wherein M² is zirconium or hafnium; (X⁵) and(X⁶) are independently a cyclopentadienyl, an indenyl, a substitutedcyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸) areindependently a hydrocarbyl group having up to 12 carbon atoms, H, BH₄,F, Cl, Br, or I, wherein at least one of (X⁷) and (X⁸) is a hydrocarbylgroup, H, or BH₄; and any substituent on the substitutedcyclopentadienyl or substituted indenyl is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, any of which having from 1 to 20 carbon atoms.
 27. Acatalyst composition according to claim 25, wherein the metallocene(X⁹)(X¹⁰)(X¹¹)(X¹²)M³ (M3-C) has the formula:(X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-D), wherein M³ is zirconium or hafnium; (X⁹)is a substituted cyclopentadienyl group, wherein any substituent isindependently a linear or branched alkyl group having from 1 to 12carbon atoms; (X¹⁰) is a substituted indenyl group, wherein anysubstituent is independently an aliphatic group, an aromatic group, or acombination of aliphatic and cyclic groups, any of which having from 1to 20 carbon atoms; and (X¹¹) and (X¹²) are independently a hydrocarbylgroup having up to 12 carbon atoms, H, BH₄, F, Cl, Br, or I, wherein atleast one of (X¹¹) and (X¹²) is a hydrocarbyl group, H, or BH₄.
 28. Acatalyst composition according to claim 25, wherein the at least onesecond metallocene comprises an unbridged metallocene having theformula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-D), wherein M² is zirconium or hafnium; (X⁵)and (X⁶) are independently a cyclopentadienyl, an indenyl, a substitutedcyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸) areindependently a hydrocarbyl group having up to 12 carbon atoms, H, BH₄,F, Cl, Br, or I, wherein at least one of (X⁷) and (X⁸) is a hydrocarbylgroup, H, or BH₄; and any substituent on the substitutedcyclopentadienyl or substituted indenyl is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, any of which having up from 1 to 20 carbon atoms;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-D),  wherein M³ is zirconium or hafnium;(X⁹) is a substituted cyclopentadienyl group, wherein any substituent isindependently a linear or branched alkyl group having from 1 to 12carbon atoms; (X¹⁰) is a substituted indenyl group, wherein anysubstituent is independently an aliphatic group, an aromatic group, or acombination of aliphatic and cyclic groups, any of which having from 1to 20 carbon atoms; and (X¹¹) and (X¹²) are independently a hydrocarbylgroup having up to 12 carbon atoms, H, BH₄, F, Cl, Br, or I, wherein atleast one of (X¹¹) and (X¹²) is a hydrocarbyl group, H, or BH₄; or iii)any combination thereof.
 29. A catalyst composition according to claim25, wherein: a) the at least one first metallocene comprises a compoundhaving the formula:

 wherein M^(1A) is zirconium or hafnium; X^(3A) and X^(4A) areindependently F, Cl Br, I, benzyl, phenyl, or methyl, wherein at leastone of X^(3A) and X^(4A) is benzyl, phenyl, or methyl; E^(A) is C or Si;R^(1A) and R^(2A) are independently an alkyl group or an aryl group,either of which having up to 12 carbon atoms, or hydrogen, wherein atleast one of R^(1A) and R^(2A) is an aryl group; R^(3A) and R^(4A) areindependently H or CH₃; n is an integer from 0 to 5, inclusive; andR^(5A) and R^(6A) are independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 12 carbon atoms; or hydrogen; b) the at least onesecond metallocene comprises a compound having the formula: i)

 or any combination thereof, wherein M^(2A) is, independently, zirconiumor hafnium; X^(7A) and X^(8A), in each occurrence, are in dependently F,Cl, Br, I, benzyl, phenyl, or methyl, wherein at least one of X^(7A) andX^(8A) is benzyl, phenyl, or methyl; R^(7A) and R^(8A), in eachoccurrence, are independently H, methyl, ethyl, n-propyl, n-butyl,n-pentyl, CH₂CH₂CH₂Ph, CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂; ii)

 wherein M^(3A) is zirconium or hafnium; R^(9A) is H or CH₃; R^(10A) isH, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, orCH₂CH₂CH₂CH₃; and X^(11A) and X^(12A) are independently F, Cl, Br, I,benzyl, phenyl, or methyl, wherein at least one of X^(11A) and X^(12A)is benzyl, phenyl, or methyl; or iii) any combination thereof; and c)the at least one activator-support comprises a solid oxide treated withan electron-withdrawing anion, wherein: the solid oxide is silica,alumina, silica-alumina, aluminophosphate, aluminum phosphate, zincaluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zincoxide, mixed oxides thereof, or any combination thereof; and theelectron-withdrawing anion is fluoride, chloride, bromide, iodide,phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate,trifluoroacetate, phosphate, fluorophosphate, fluorozirconate,fluorosilicate, fluorotitanate, permanganate, substituted orunsubstituted alkanesulfonate, substituted or unsubstitutedarenesulfonate, or any combination thereof.
 30. A process for producinga composition comprising contacting: 1) at least one first metallocene;2) at least one second metallocene; and 3) at least oneactivator-support, wherein: a) the at least one first metallocenecomprises an ansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-A),  wherein M¹ is titanium, zirconium, orhafnium; (X¹) and (X²) are independently a substituted cyclopentadienyl,a substituted indenyl, or a substituted fluorenyl; one substituent on(X¹) and (X²) is a bridging group having the formula ER¹R², wherein E isa carbon atom, a silicon atom, a germanium atom, or a tin atom, and E isbonded to both (X¹) and (X²), and wherein R¹ and R² are independently analkyl group or an aryl group, either of which having up to 12 carbonatoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;at least one substituent on (X¹) or (X²) is a substituted or anunsubstituted alkenyl group having up to 12 carbon atoms; (X³) and (X⁴)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl, substituted indenyl, substituted fluorenyl, orsubstituted alkenyl group is independently an aliphatic group, anaromatic group, a cyclic group, a combination of aliphatic and cyclicgroups, an oxygen group, a sulfur group, a nitrogen group, a phosphorusgroup, an arsenic group, a carbon group, a silicon group, or a borongroup, any of which having from 1 to 20 carbon atoms; a halide; orhydrogen; b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-A),  wherein M² is titanium, zirconium, orhafnium; (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,a substituted cyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(B) ₂ or SO₃R^(B) wherein R^(B)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any substituent on the substituted cyclopentadienyl orsubstituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 20 carbon atoms; a halide; or hydrogen;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-A),  wherein M³ is titanium, zirconium,or hafnium; (X⁹) is a substituted cyclopentadienyl group, wherein onesubstituent is an aliphatic group, an aromatic group, or a combinationof aliphatic and cyclic groups, any of which having up to 20 carbonatoms; (X¹⁰) is a substituted indenyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms; (X¹¹) and(X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(C) ₂ or SO₃R^(C), wherein R^(C)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl or substituted indenyl is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, ora boron group, any of which having from 1 to 20 carbon atoms; a halide;or hydrogen; or iii) any combination thereof; and c) the at least oneactivator-support comprises a solid oxide treated with anelectron-withdrawing anion.
 31. A process for producing a polymerizationcatalyst composition comprising contacting: 1) at least one firstmetallocene; 2) at least one second metallocene; 3) optionally, at leastone organoaluminum compound; and 4) at least one activator-support,wherein: a) the at least one first metallocene comprises anansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-A),  wherein M¹ is titanium, zirconium, orhafnium; (X¹) and (X²) are independently a substituted cyclopentadienyl,a substituted indenyl, or a substituted fluorenyl; one substituent on(X¹) and (X²) is a bridging group having the formula ER¹R², wherein E isa carbon atom, a silicon atom, a germanium atom, or a tin atom, and E isbonded to both (X¹) and (X²), and wherein R¹ and R² are independently analkyl group or an aryl group, either of which having up to 12 carbonatoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;at least one substituent on (X¹) or (X²) is a substituted or anunsubstituted alkenyl group having up to 12 carbon atoms; (X³) and (X⁴)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl, substituted indenyl, substituted fluorenyl, orsubstituted alkenyl group is independently an aliphatic group, anaromatic group, a cyclic group, a combination of aliphatic and cyclicgroups, an oxygen group, a sulfur group, a nitrogen group, a phosphorusgroup, an arsenic group, a carbon group, a silicon group, or a borongroup, any of which having from 1 to 20 carbon atoms; a halide; orhydrogen; b) the at least one second metallocene comprises an unbridgedmetallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-A),  wherein M² is titanium, zirconium, orhafnium; (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,a substituted cyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(B) ₂ or SO₃R^(B) wherein R^(B)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any substituent on the substituted cyclopentadienyl orsubstituted indenyl is independently an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, or a boron group, any ofwhich having from 1 to 20 carbon atoms; a halide; or hydrogen;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-A),  wherein M³ is titanium, zirconium,or hafnium; (X⁹) is a substituted cyclopentadienyl group, wherein onesubstituent is an aliphatic group, an aromatic group, or a combinationof aliphatic and cyclic groups, any of which having up to 20 carbonatoms; (X¹⁰) is a substituted indenyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms; (X¹¹) and(X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(C) ₂ or SO₃R^(C), wherein R^(C)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; and any additional substituent on the substitutedcyclopentadienyl or substituted indenyl is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, ora boron group, any of which having from 1 to 20 carbon atoms; a halide;or hydrogen; or iii) any combination thereof; c) the at least oneorganoaluminum compound comprises a compound having the formula:Al(X¹³)_(n)(X¹⁴)_(3-n), wherein (X¹³) is a hydrocarbyl having from 1 to20 carbon atoms; (X¹⁴) is an alkoxide or an aryloxide, any of whichhaving from 1 to 20 carbon atoms, halide, or hydride; and n is a numberfrom 1 to 3, inclusive; and d) the at least one activator-supportcomprises a solid oxide treated with an electron-withdrawing anion;wherein the at least one organoaluminum compound is optional when atleast one of the following conditions exist: 1) a) at least one of (X³)and (X⁴) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;b) at least one of (X⁷) and (X⁸) is a hydrocarbyl group having up to 20carbon atoms, H, or BH₄; and c) at least one of (X¹¹) and (X¹²) is ahydrocarbyl group having up to 20 carbon atoms, H, or BH₄; 2) thecatalyst composition comprises at least one organoaluminoxane compound;or 3) both conditions 1 and 2 exist.
 32. A process for producing apolymerization catalyst composition comprising contacting: 1) at leastone first metallocene; 2) at least one second metallocene; and 3) atleast one activator-support, wherein: a) the at least one firstmetallocene comprises an ansa-metallocene having the formula:(X¹)(X²)(X³)(X⁴)M¹  (M1-B),  wherein M¹ is titanium, zirconium, orhafnium; (X¹) and (X²) are independently a substituted cyclopentadienyl,a substituted indenyl, or a substituted fluorenyl; one substituent on(X¹) and (X²) is a bridging group having the formula ER¹R², wherein E isa carbon atom, a silicon atom, a germanium atom, or a tin atom, and E isbonded to both (X¹) and (X²), and wherein R¹ and R² are independently analkyl group or an aryl group, either of which having up to 12 carbonatoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;at least one substituent on (X¹) or (X²) is a substituted or anunsubstituted alkenyl group having up to 12 carbon atoms; (X³) and (X⁴)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(A) ₂ or SO₃R^(A), wherein R^(A)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; wherein at least one of (X³) and (X⁴) is a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; and any additional substituenton the substituted cyclopentadienyl, substituted indenyl, substitutedfluorenyl, or substituted alkenyl group is independently an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, ora boron group, any of which having from 1 to 20 carbon atoms; a halide;or hydrogen; b) the at least one second metallocene comprises anunbridged metallocene having the formula:i) (X⁵)(X⁶)(X⁷)(X⁸)M²  (M2-C),  wherein M² is titanium, zirconium, orhafnium; (X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl,a substituted cyclopentadienyl, or a substituted indenyl; (X⁷) and (X⁸)are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having upto 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(B) ₂ or SO₃R^(B), wherein R^(B)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; wherein at least one of (X⁷) and (X⁸) is a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; and any substituent on thesubstituted cyclopentadienyl or substituted indenyl is independently analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, or a boron group, any of which having from 1 to 20 carbon atoms;a halide; or hydrogen;ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³  (M3-C),  wherein M³ is titanium, zirconium,or hafnium; (X⁹) is a substituted cyclopentadienyl group, wherein onesubstituent is an aliphatic group, an aromatic group, or a combinationof aliphatic and cyclic groups, any of which having up to 20 carbonatoms; (X¹⁰) is a substituted indenyl group, wherein one substituent isan aliphatic group, an aromatic group, or a combination of aliphatic andcyclic groups, any of which having up to 20 carbon atoms; (X¹¹) and(X¹²) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; 3) a hydrocarbyloxide group, ahydrocarbylamino group, or a trihydrocarbylsilyl group, any of whichhaving up to 20 carbon atoms; or 4) OBR^(C) ₂ or SO₃R^(C), wherein R^(C)is an alkyl group or an aryl group, any of which having up to 12 carbonatoms; wherein at least one of (X¹¹) and (X¹²) is a hydrocarbyl grouphaving up to 20 carbon atoms, H, or BH₄; and any additional substituenton the substituted cyclopentadienyl or substituted indenyl isindependently an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, or a boron group, any of which having from 1 to20 carbon atoms; a halide; or hydrogen; or iii) any combination thereof;and c) the at least one activator-support comprises a solid oxidetreated with an electron-withdrawing anion.
 33. A composition accordingto claim 18, wherein: a) the at least one first metallocene comprises acompound having the formula:

 wherein M^(1B) is zirconium or hafnium; R^(2B) is methyl or phenyl;R^(3B) and R^(4B) are independently H or CH₃; and n is an integer from 0to 5, inclusive; b) the at least one second metallocene comprises acompound having the formula:

 or any combination thereof, wherein M^(2B) is zirconium or hafnium;X^(7B) and X^(8B) are independently benzyl, Cl, or methyl; and R^(7B)and R^(8B) are independently H, methyl, ethyl, n-propyl, n-butyl,CH₂CH═CH₂, CH₂CH₂CH═CH₂, or CH₂CH₂CH₂CH═CH₂; c) the at least oneactivator-support is chlorided alumina, fluorided alumina, sulfatedalumina, fluorided silica-alumina, or any combination thereof; and d)the at least one organo aluminum compound is triethylaluminum,tributylaluminum, triisobutylaluminum, or any combination thereof.
 34. Acomposition according to claim 18, wherein: a) the at least one firstmetallocene comprises a compound having the formula:

 wherein M^(1B) is zirconium or hafnium; R^(2B) is methyl or phenyl;R^(3B) and R^(4B) are independently H or CH₃; and n is an integer from 0to 5, inclusive; b) the at least one second metallocene comprises acompound having the formula:

 wherein M^(3B) is zirconium or hafnium; R^(9B) is H or CH₃; and R^(10B)is H, CH₂CH═CH₂, CH₂CH₂CH═CH₂, CH₂CH₂CH₂Ph, or CH₂CH₂CH₂CH₃; c) the atleast one activator-support is chlorided alumina, fluorided alumina,sulfated alumina, fluorided silica-alumina, or any combination thereof;and d) the at least one organoaluminum compound is triethylaluminum,tributylaluminum, triisobutylaluminum, or any combination thereof.
 35. Acomposition according to claim 18, wherein the contact product furthercomprises at least one organoaluminoxane compound, at least oneorganoboron or organoborate compound, or a combination thereof.
 36. Acomposition according to claim 18, wherein the at least one firstmetallocene comprises a compound having the formula:

wherein M^(1A) is titanium, zirconium, or hafnium; X^(3A) and X^(4A) areindependently Cl or Ph; E^(A) is C or Si; R^(1A) and R^(2A) are Ph;R^(3A) and R^(4A) are independently H or CH₃; n is an integer from 0 to5, inclusive; and R^(5A) and R^(6A) are t-Bu.
 37. A compositionaccording to claim 1, wherein the at least one first metallocenecomprises a compound having the formula:

wherein M^(1A) is titanium, zirconium, or hafnium; X^(3A) and X^(4A) areindependently Cl or Ph; E^(A) is C or Si; R^(1A) and R^(2A) are Ph;R^(3A) and R^(4A) are independently H or CH₃; n is an integer from 0 to5, inclusive; and R^(5A) and R^(6A) are t-Bu.